The midfielder spearheaded a ruthless attacking display and was involved in every goal, providing three assists in the opening 45 minutes, before deservedly getting on the score sheet himself with a curling effort.
It was a captain's performance from De Bruyne, whose remarkably precise delivery ensured he was creator in chief at Hampden Park.
But his first contribution was all about desire.
A surging run through midfield left Scotland defenders in his wake, before he squared to give Romelu Lukaku the simplest of finishes just 14 seconds after the hosts had taken a free-kick deep in Belgium territory.
He whipped in a pinpoint cross from the right for the second, which Thomas Vermaelen steered home from six yards and Toby Alderweireld made it three with a header on the half hour mark, after De Bruyne picked him out from a corner.
And then it was his turn, collecting a pass from Lukaku and wrapping his right foot around the ball to guide it into the bottom right corner.
De Bruyne tucks in Belgium's fourth.— Sky Sports Football (@SkyFootball) September 9, 2019
A night to forget for Scotland.
Watch the final minutes of Scotland 0-4 Belgium live on Sky Sports Football or follow here: https://t.co/Pei81ROQi4 pic.twitter.com/sOjaVHHHii
It was a masterclass from De Bruyne, who has recorded eight assists and scored two goals in his last six matches for club and country.
South of the border, Phil Foden was another City player to enjoy a fruitful night in his nation’s jersey.
He started and scored both goals in England U21s' 2-0 victory over Kosovo, where he showed a canny knack for being in the right place at the right time.
The Stockport-born teenager tapped home after Steven Sessegnon’s shot was blocked on the line for his first, while the second was fired into the top corner when Rhian Brewster's blocked cross fell kindly into his path 10 yards out.
That build-up play 😍— Football on BT Sport (@btsportfootball) September 9, 2019
England U21 rack up the passes as Phil Foden opens the scoring. pic.twitter.com/mEa27hnLM2
Riyad Mahrez was the final City player in action as Algeria hosted a friendly against Benin, their first match since being crowned African Cup of Nations champions this summer.
Mahrez captained the side and played 77 minutes in what proved to be a happy homecoming, with an Islam Slimani penalty enough for a 1-0 win.
It was a game the Desert Foxes dominated and the 28-year-old nearly made sure all of City’s internationals found the back of the net on Monday evening, but the Benin keeper was equal to his volley from the edge of the area.