De Bruyne skippered the Red Devils in the Wembley clash while Walker, on what was his 50th cap, was deployed in a back three for England – and both made key contributions in what was an intriguing encounter with the Three Lions coming from behind to inflict a first loss on Belgium in two years.
It was De Bryune who was the alchemist behind Belgium’s impressive opening 45 minutes and the City midfielder’s vision instigated the move that saw the visitors take a 15th minute lead from the penalty spot after Romelu Lukaku was brought down by Eric Dier.
The Inter Milan striker then coolly converted the spot kick as a fluid and confident Belgium demonstrated just why they are ranked as the number country in the world according to the latest FIFA rankings.
England keeper Jordan Pickford then produced a fine save to prevent De Bruyne doubling Belgium’s lead before, somewhat against the run of play, Gareth Southgate’s side drew level with the game’s second penalty four minutes before the break.
Marcus Rashford converted from the spot for his fourth consecutive international goal after England skipper Jordan Henderson had been impeded in the box.
England then took a somewhat fortuitous second half lead after Mason Mount’s shot took a huge deflection off Toby Alderweireld and spiralled over Simon Mignolet.
Belgium should have drawn level after De Bruyne then delivered the pass of the night, raking in a laser-guided ball with the outside of the boot from the left flank to put Yannick Carrasco in one on one with England 'keeper Pickford.
However, the striker could only stab the effort wide with De Bruyne then substituted by Martinez after another impressive display.
Walker capped another impressive night's work with a vital block to deny Lukaku late in the second half before substitute Harry Kane spurned a golden chance to head home a third goal for England.
The Three Lions held on though to secure the win over the FIFA’s number one ranked country and so move top of Group A2 with seven points from three games – one ahead of Belgium.
Meanwhile, City defender Nathan Ake came on as late second half substitute as the Netherlands drew 0-0 away to Bosnia and Herzegovina in their latest Group A1 encounter.