Despite England having enjoyed strong spells throughout the game, missing noticeable chances in the first-half, it was to be Podolski's night as he struck a fantastic winner that left Joe Hart well beaten.
Three at the back looked promising for England
Whilst the pre-game amble was dominated by presentations and tributes to Podolski, it was interesting to see Gareth Southgate opting with a three-man defensive formation when the teams came out.
Kyle Walker and Ryan Bertrand were picked to flank the three centre-backs, with both Michael Keane and Jake Livermore selected for debuts.
There was almost a fairytale beginning for Burnley's Keane, who rifled a loose ball narrowly over the bar from a corner won by some persistent attacking by Jamie Vardy, who had penalty appeals quashed after going down under the challenge of Marc Andre ter-Stegen.
Podolski, looking to find international goal number 49 on a special evening for himself, had an effort blocked by Keane, whilst the closest either side went in the opening half hour was through Adam Lallana.
Lallana hits post, Alli hits ter-Stegen
Capitalising on a lax pass in the Germany midfield to skip past Antonio Rudiger, Lallana embarked on a lung-busting sprint towards the Germany penalty area, where he'd beat ter-Stegen with a shot across goal, only for the ball to hit the post.
As Podolski and Dier both lashed chances over the bar, it looked like the first-half just wasn't going to see a goal, something that Dele Alli aided the idea of by missing a sitter soon after. Good pressing saw Vardy given the option to prod the ball to Alli unmarked in the area, ter-Stegen winning the mental battle as he stood tall and stopped a shot placed straight at him.
Germany had floated through the half in first gear but were almost woke up when play resumed, as reported Liverpool target Julian Brandt lashed an effort wide following Joe Hart's poor punch.
Dele Alli had another chance to open the scoring from a Vardy cross, after lovely work from Livermore, but again his touch was off as he skewed an effort towards ter-Stegen.
On a night where little was seemingly being learnt, Alli and Lallana's link-up play was offering a promising sign for Southgate, whilst Vardy's nuisance of a presence up front continued to trouble the German back-line.
However, with a little over 20 minutes to go, Lukas Podolski opened the scoring on a night where it seemed written in the stars for him to score.
A patient German move saw them pass the ball around the back before quickly pushing it through the centre of the pitch, Podolski dropping his shoulder on the edge of the box before hammering the ball into the top-left corner with that dangerous left foot of his.
With three England changes denting their attacking momentum, Germany took the momentum and almost had a second when Keane let Leroy Sane in, only for Joe Hart to save the ball brilliantly.
The Three Lions would struggle to create anything for the remainder of the evening, with Andre Schurrle close to making it two up at the other end, his shot deflected wide off John Stones.
That proved to be the final meaningful effort of the night, with Germany running the clock down in typically efficient style to seal a win in Dortmund.