After a tournament which promised so much, England are heading home from the World Cup empty-handed as goals from Thomas Meunier and Eden Hazard were enough to secure a third-placed finish for the Red Devils.
There was nothing Pickford could do though as De Bruyne and Hazard combined to wrap up the victory on 82 minutes, the latter drilling low inside the near post for his third goal of the competition.
Belgium can take pride in achieving its best-ever finish in a World Cup, but unlike England, youth is not necessarily on this team's side.
At least Kane is a step nearer the Golden Boot, after closest rival Romelu Lukaku, two goals behind, appeared to have lead in his despite having the chances he needed to draw level before he was substituted on the hour-mark.
Both Belgium and England started the tournament in Group G. The two teams previously played each other in a group round match on June 28.
Kane has six goals, despite sitting out England's final group game, a 1-0 loss to Belgium. A similar outing as the one in England's previous tie against Belgium should help him cement his place in Gareth Southgate's squad for a long time.
To watch a preview of Saturday's Belgium vs. England World Cup third-place playoff match, check out the video below, courtesy of the Radio Times.
The goal means Belgium have had 10 different goalscorers at this World Cup - equaling the record set by France in 1982 and Italy in 2006. All three of those "internet TV" services require credit card information and subscription fees, but they all offer seven-day free trial periods.
Hello! And welcome to our live coverage of this afternoon's World Cup third place play-off.
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Where Belgium go from here largely depends on how many of Roberto Martinez's older players are able to hang on for another crack at a major tournament.
"It's the chance to have our second-best-ever finish and the chance for the players to get a medal", Southgate was quoted as saying by The Guardian. Belgium won that encounter in Kaliningrad 1-0 thanks to a curled shot from Adnan Januzaj.
And that perhaps wasn't the best approach to take as Belgium looked set to go for the kill from the get-go.
"Sometimes it's not always a good decision for people to play if their energy isn't quite there and we've got to think about who can give us the best performance", he said.
With England pushing forward, Meunier almost produced one of the goals of the tournament, his crisp volley from a Dries Mertens cross drawing an excellent one-handed stop from Pickford.
It desperately needed changing and the introduction of Jesse Lingard and Marcus Rashford at the break added fresh life.
Defenders: Toby Alderweireld (Tottenham), Thomas Meunier (Paris Saint-Germain), Thomas Vermaelen (Barcelona), Jan Vertonghen (Tottenham), Dedryck Boyata (Celtic), and Vincent Kompany (Manchester City).
Keep it right here for score updates, analysis and highlights from Belgium vs. England.
But it mattered little in the end, Hazard making no mistake with his near-post finish having been sent clean through by De Bruyne, the star pair combining to put a fitting seal on Belgium's impressive showing in Russian Federation.