They will learn of their opponents on Friday but after the third qualifying round drew to a close on Wednesday, know it will be one of OGC Nice, TSG 1899 Hoffenheim, BSC Young Boys, Steaua București or İstanbul Başakşehir.
The Reds are seeded alongside Napoli, Sevilla, CSKA Moscow and Sporting CP as a result of their UEFA co-efficient - ensuring a slightly less daunting draw.
Several tricky teams await the Reds
Their pool of opponents presents the chance of a reunion with former striker Mario Balotelli, who left Liverpool for Nice upon the expiry of his contract 12 months ago.
The Ligue 1 club - who finished third last year behind only winners AS Monaco and runners-up Paris Saint-Germain - also have Dante and highly-rated midfielder Jean Michaël Seri and would be arguably Liverpool's toughest potential assignment.
Roberto Firmino's former club Hoffenheim could present another difficult opponent after finishing fourth in the Bundesliga last season in 30-year-old Julian Nagelsmann's first full season as manager.
Die Kraichgauer have signed ex-Arsenal winger Serge Gnabry this summer as they look to build on last season's success, while former Leicester City striker Andrej Kramarić is one of their chief threats and scored 15 league goals last term.
Liverpool would inevitably prefer to face a team such as Young Boys, who they took on in the 2012-13 Europa League group stages - drawing 2-2 at Anfield and winning 5-3 away in Switzerland.
The Merseyside outfit faced Steaua in 2010, also in the Europa League, thrashing the Romanian team 4-1 at Anfield and drawing 1-1 away to secure progression to the knockout rounds.
The most familiar names in Young Boys' squad are young defender Kevin Mbabu, who joined on a permanent three-year deal from Newcastle United this summer, and ex-Ajax and Benfica midfielder Miralem Sulejmani.
Liverpool's other potential opponent, İstanbul BB, finished second in Turkish Süper Lig last season - four points off title-winners Beşiktaş and have never faced Liverpool before in any competition.
The Turkish team have former Manchester City and Arsenal duo Gaël Clichy and Emmanuel Adebayor among their ranks, as well as former Leicester midfielder Gökhan Inler and ex-Southampton wide-man Eljero Elia.
Jürgen Klopp's side will only learn whether they are home or away in the first-leg when the draw is made, at 11am in Nyon on Friday.
The first-leg will be played on either Tuesday 15 or Wednesday 16 August, after their Premier League opener at Watford and before the visit of Crystal Palace to Anfield.
The second-leg follows the clash with Palace on Tuesday 22 or Wednesday 23 August, preceding a huge Anfield clash with Arsenal.
Liverpool are competing to play in the Champions League group stages for just the second time in eight years, having finished third in their group in their last campaign under Brendan Rodgers in 2014-15.
Seeded play-off draw teams:
Liverpool, Sevilla, Napoli, CSKA Moscow, Sporting CP.
Unseeded play-off draw teams:
Steaua Bucharest, Young Boys, Nice, Hoffenheim, İstanbul BB.