It was England's first ever knockout round win at the Euros inside 90 minutes and after a build-up dominated by talk of historic and bitter tournament losses to Germany, their focus will now be on making some history of their own.
The visitors' defeat marked the end of Joachim Loew's time as Germany coach after 15 years in charge, during which he guided them to the 2014 World Cup title in Brazil.
The goals came after midfielder Jack Grealish was introduced in the 69th minute when the entire tempo and mood of the game changed.
Six minutes after Grealish came on he was involved in a flowing passing move which ended with left wing back Luke Shaw deftly slipping the ball across the face of the goal for Sterling to slide in his third goal in four Euro 2020 games.
Yet shortly after scoring Sterling almost gifted the Germans a leveller when he gave the ball away on the halfway line and Kai Havertz sent Thomas Mueller through on goal.
The experienced World Cup winner had only England keeper Jordan Pickford to beat but dragged his shot wide of his right-hand post, leaving Sterling, who watched in anguish on his knees, to leap to his feet in relief.
After that reprieve, and with the crowd roaring England on, Grealish was the direct provider for the second goal, crossing from the left for captain Kane to beat keeper Manuel Neuer with a stooping header.
It was Kane's first goal of the tournament and his return to scoring ways will be another positive for England manager Gareth Southgate as he looks ahead at a potential route to the final.
Soccer Football - Euro 2020 - Round of 16 - England v Germany - Wembley Stadium, London, Britain - June 29, 2021 England's Harry Kane scores their second goal. (Photo: Reuters)
CAUTIOUS LINEUP
Southgate's decision to play a five-man defence and two holding midfielders was a cautious one, but England did start the game brightly.
Sterling tested Neuer in the 16th minute, cutting in from the left flank and finding room to unleash a drive towards the far corner which the German keeper did well to get across to.
Much of England's probing was coming from Kieran Trippier down the right and he found Harry Maguire in a promising position with a lofted ball to the back post but the centre half's header was over the bar.
Germany were enjoying plenty of possession in midfield with England sitting deep but they provided a warning of their threat when Kai Havertz slipped through Timo Werner, although Pickford was out quickly to smother.
Just before the break Mats Hummels had to intervene quickly to clear as Kane looked to pounce after Sterling's burst into the box had caused chaos.
After the interval Germany sensed England had lost their way and went close when Havertz's powerful drive was superbly tipped over by Pickford.
The game was in the balance but then came Grealish, whose name had been sung by the England fans throughout the game and who lived up to those hopes and expectations by providing the spark England had been missing.
England will head into their quarter-final in Rome on Saturday knowing victory will set-up a semi and potentially a final on home turf back at Wembley.
"We don't want to get too ahead of ourselves but it is a massive game," said midfielder Declan Rice.
"The dressing room, I have not been a part of a team with this togetherness. We really believe, with the tournament being at Wembley."
"It's incredible, a lot of people had written us off in the group stage, complaints about the performances, not scoring enough but we wanted to prove people wrong, with a full house everyone had the fire in the belly to one, knock Germany out and two progress in the tournament," he added.
