In the first domestic cup final of the season, Klopp has reached a cup final for his fifth successive season as a manager - and he'll be hoping for a more enjoyable afternoon this time around after losing his last three finals at Borussia Dortmund.
But they come up against a City side buoyant from their emphatic 3-1 UEFA Champions League last 16 first-leg win away at Dynamo Kyiv, with their squad undoubtedly keen to send Manuel Pellegrini off with at least one piece of silverware, the 68-year-old being replaced by Pep Guardiola in the summer.
Having narrowly earned their way into the last 16 of the UEFA Europa League just a few days ago, before being rewarded with a mouthwatering two-legged tie against rivals Manchester United, Liverpool will be hoping to add some gloss to what has been a frustratingly inconsistent campaign until now.
Although they could narrow the gap between themselves and the Barclays Premier League's top-four with a win over City at Anfield on Wednesday - it seems that the cup competitions are where their chances of turning a largely forgettable season into a memorable one.
Of course, that starts with Sunday's final - which Klopp has repeatedly spoken of his desire to win, with the benefits that would present to his young and inexperienced squad obvious. Success breeds success, something the German will likely be stressing in the Wembley changing rooms to his squad before kick-off.
The players, too, will be hoping to prove a point. The Reds fell at the semi-final stage of both the Capital One Cup and the FA Cup last season and will be hoping to avenge their disappointing last trip to Wembley, which saw them dismally beaten 2-1 by Aston Villa.
As such, they will be treating this competition just as seriously as they have seemed to throughout their run to the final - with only a hectic schedule and a depleting bout of injuries preventing Klopp from going full-strength in the earlier rounds.
The Reds will also take confidence from their previous meeting with City this season, undoubtedly the highlight of Klopp's short Merseyside tenure so far, as a side inspired by Roberto Firmino and Philippe Coutinho romped to a 4-1 win at the Etihad Stadium.
The highlights of that match will be played regularly prior to Sunday's showpiece, but Klopp and co. will know they face a tougher City side this time around - although they too welcome some important players back to the team, those who were out injured back in November.
With both sides set to field their strongest possible sides, the latest edition of the League Cup final - so often derided as 'the Mickey Mouse Cup' and the less important competition in comparison to the FA Cup - and the 55th of its history, is set to be an incredibly exciting one.
The depth of talent and quality within both sides ensures that this one is finely hung in the balance, and Liverpool will have to be at their very best throughout in order to end their four-year wait for silverware.
Central to that will be Klopp's gegenpressing style, which has had hits-and-misses this season as his players come to grips with the German's style. City was one such highlight, as was a ruthless recent 6-0 win at Aston Villa, but other flat performances at Watford, Newcastle United and West Ham United have shown the other side at the spectrum.
The Reds boss will surely not allow anything but 110 per cent effort from his side on one of the widest pitches in the country, if not in Europe, at Wembley - on what is expected to be another tense, and unpredictable, afternoon.
Adam Lallana, Joe Allen and Martin Škrtel all made their returns from injury to take part in training earlier in the week, but are unlikely to be in the starting line-up.
Neither have featured since their 2-2 league draw with Sunderland on February 6, with Lallana struggling with a calf injury and Allen having suffered a hamstring problem.
Škrtel, meanwhile, made his return to first-team training from a hamstring injury that had kept him sidelined since limping off in the defeat at Watford on December 20, whilst fellow defender Dejan Lovren returned from illness to train.
Kevin Stewart, who recently signed a new contract after impressing in the FA Cup, misses out with an ankle ligament issue whilst long-term absentees Jordan Rossiter (hamstring), Danny Ings and Joe Gomez (both anterior cruciate ligaments) remain sidelined.
After Lucas Leiva came in at centre-back on Thursday, Klopp is expected to make just the single change to his team for the fourth consecutive game - with ex-City defender Kolo Touré the favourite to partner Mamadou Sakho in the heart of defence.
James Milner and Daniel Sturridge are also expected to line up against their former employers, with the striker likely to form an exciting triumvirate alongside Roberto Firmino and Philippe Coutinho, who has scored four goals in six appearances against City.
Despite a troubling heel problem that has hampered his form, and kept him out for long periods earlier in the season, Reds skipper Jordan Henderson is expected to lead his teammates out of the tunnel at the national stadium.
Klopp's opposite, Manuel Pellegrini, is without a number of first-choice options - with Kevin De Bruyne, who has five goals in this competition this term, still out with a knee injury.
Fabian Delph (calf) and Samir Nasri (hamstring) are also unavailable, although Wilfried Bony (calf), Jesús Navas and Eliaquim Mangala (both hamstring) are expected to return to the fold.
Pellegrini will also hope to have captain Vincent Kompany fully fit, with the Chilean boss also confident of having Raheem Sterling and Bacary Sagna - who trained separately on Friday - in the squad after having recovery sessions.
Road to Wembley:
Third round: Liverpool 1-1 Carlisle United AET (Ings) - (3-2 on pens)
Fourth round: Liverpool 1-0 Bournemouth (Teixeira)
Fifth round: Southampton 1-6 Liverpool (Sturridge x2, Origi x3, Ibe)
Semi-final first-leg: Stoke City 0-1 Liverpool (Ibe)
Semi-final second-leg: Liverpool 0-1 Stoke City AET (6-5 on pens)
Third round: Sunderland 1-4 Manchester City (Agüero, De Bruyne, Mannone og, Sterling)
Fourth round: Manchester City 5-1 Crystal Palace (Bony, De Bruyne, Iheanacho, Touré, Garcia)
Fifth round: Manchester City 4-1 Hull City (Bony, Iheanacho, De Bruyne x2)
Semi-final first-leg: Everton 2-1 Manchester City (Navas)
Semi-final second-leg: Manchester City 3-1 Everton (Fernandinho, De Bruyne, Agüero)
At Anfield: Liverpool - 50 wins, Draws - 19, Manchester City - 13 wins.
At the Etihad Stadium: Manchester City - 28 wins, Draws - 22, Liverpool - 33 wins.
Overall: Liverpool - 84 wins, Draws - 44, Manchester City - 44 wins.
Last meeting: Manchester City 1-4 Liverpool, Barclays Premier League, 21st November 2015.
Form in Premier League: LWLDW
Form in all competitions: DLWDW
Form in Premier League: WDWLL
Form in all competitions: WLLLW
Sunday marks Liverpool's 12th League Cup final, a record for the competition. They've won eight of their 11 finals since 1981, with their triumph over Cardiff City on penalties in 2012 their most recent win.
City, meanwhile, have won the competition on three occasions - losing just one final. Having won it in 1970, 1976 and most recently in 2014, they finished runners-up in 1974.
This is the first time the two teams have met in the final of any competition and their first competitive fixture at a neutral venue, although Liverpool are the designated home team.
Liverpool haven't lost a domestic cup game against City in their last eight, a record stretching back to an FA Cup fourth-round replay defeat in 1973. They've won six and drawn twice since.
City have only beaten Liverpool once in their six League Cup meetings, a 3-2 round three win in 1969/70 when they went onto lift the trophy (D2 L3).
Jürgen Klopp has been in a final of a cup competition in all of his last five seasons as manager, losing the Champions League final in 2013, as well as German Cup final defeats in 2014 and 2015, after winning the DFB Cup in 2012.
In the last eight meetings between Liverpool and City, 32 goals have been scored with both teams finding the back of the net.
Only three players who played in Liverpool’s last League Cup final four years ago are still at the club - Martin Škrtel, Jordan Henderson and José Enrique. The Slovakian centre-back scored Liverpool’s first goal on that day.
City have scored 17 times in reaching the League Cup final, with nine different City players scoring in this year’s competition (plus a single own goal).
Both teams have scored in each of City’s five League Cup games this season.
Both teams have scored in all four of Liverpool’s visits to the new Wembley Stadium.
All three of the goals that Liverpool have conceded in this year’s competition have come before half-time.
There has been at least one goal in each half in 10 of the last 11 League Cup finals, with a 0-0 draw between Manchester United and Tottenham Hotspur the only exception.
Six of Liverpool’s nine League Cup goals en-route to the final came in their 6-1 thrashing of Southampton in the quarter finals.
Kevin De Bruyne has scored in all four rounds of the League Cup this season for City, with the semi-final first-leg the only game in which he didn't score.
Yaya Touré scored and assisted for Man City in their last League Cup final, when they beat Sunderland 3-1 two years ago.
Man in the middle:
Michael Oliver will referee his first League Cup final after being awarded the occasion.
The 31-year-old, part of the Select Group of Referees since 2010, became the youngest ever match official to take charge of a Premier League game the same year.
Northumberland-born Oliver has taken games at Wembley before, including the 2007 Conference National play-off final, the 2009 League One play-off final having also been fourth official for 2013 League Cup final and 2013 Community Shield final, before being the man in the middle for the 2014 Shield final.
He's taken 16 games involving Liverpool, including their last appearance at the national stadium in their disappointing 2-1 FA Cup semi-final defeat to Aston Villa back in April.
A FIFA-listed official since 2012, Oliver has overseen two games this season - a 3-1 defeat away at Manchester United and a 0-0 draw away at Arsenal.
He's also taken charge of a previous meeting between City and Liverpool, when the Sky Blues came out on top in a 3-1 home win at the start of the 2014-15 season.