The City man, Gareth Southgate’s side’s top scorer thus far, once again stepped up when it counted to grab the opening goal at Wembley Stadium.
England skipper Harry Kane then tapped home a second to put the game to bed on an historic night for the Three Lions.
But for all of our England stars' joy, there's despair for Ilkay Gundogan, whose tournament is over at the last 16 stage.
The German midfielder was an unused substitute for Die Mannschaft and England respectively, as Joachim Low’s side were edged out in the first competitive meeting between the two sides since the 2010 World Cup.
In a standout performance, it was Sterling who created the first big chance of the match, stinging the palms of Manuel Neuer after cutting inside and curling a dangerous effort towards the far post after the 15-minute mark.
That chance sprung the Three Lions into life who, before that point, had been tentatively feeling their way into the Wembley showpiece after a period of early dominance from Germany.
Despite enjoying greater territory Die Mannschaft held firm, but were thankful to Mats Hummels, whose last-ditch sliding challenge kept the scores level on the stroke of half-time.
It was Sterling once again who sparked the chance with some positive play, pouncing on a loose Thomas Muller pass and driving at the German defence before being crowded out inside the box.
The ball ricocheted into the path of Harry Kane who, instead of opting to hit it first time, looked to round the onrushing Neuer before being thwarted by Hummels’ timely interception.
Despite that chance, it was the visitors who came out of the traps the quickest once again after the restart, with Pickford needing to be at his acrobatic best to tip Havertz’s stinging drive over the bar from a knockdown before the 50-minute mark.
And Stones was at his defensive best soon after to cancel out a Germany counter, showing Timo Werner onto his left before making an important block.
It was a case of who would blink first in a cagey second half, with Southgate rolling the dice by switching Sterling over to the right flank as Jack Grealish entered the fray for Bukayo Saka.
And the decision paid dividends when the City winger cut inside and found Kane, before continuing his run into the box.
The ball eventually found its way out to Luke Shaw on the left and his low cross was calmly tapped home by Sterling to send the majority of the 40,000+ Wembley crowd into raptures.
But the game was far from over, with Muller squandering a huge opportunity with ten to play.
The Bayern Munich man, on the scoresheet in the two sides’ last competitive clash 11 years ago, was sent clean through on goal after Die Mannschaft had regained possession and launched a swift counter.
With the goal gaping, the forward’s disguised effort back across goal sent Pickford the wrong way but, agonisingly for Joachim Low’s side, wide of the post.
It was a reprieve which snapped the Three Lions back to reality, before a Kane strike dragged them once again to dreamland.
The England skipper stole a yard on the rapidly retreating German defence before heading home Grealish’s floated ball across to double Gareth Southgate’s side’s advantage and round off the scoring.
The victory sees England into the last eight, with Oleksandr Zinchenko’s Ukraine or Sweden awaiting in the next round on Saturday in Rome.