Manchester City star De Bruyne takes over from Eden Hazard, who announced his retirement from international football in December following Belgium's group stage exit at the 2022 World Cup.
That elimination marked the end of Roberto Martinez's time in charge, and De Bruyne will be tasked with leading the side under the stewardship of new coach Domenico Tedesco.
De Bruyne has won 97 caps for Belgium, scoring 25 goals.
Real Madrid goalkeeper Thibaut Courtois and striker Romelu Lukaku, on loan at Inter from Chelsea, have been named as vice-captains.
Belgium will begin its campaign to qualify for Euro 2024 on Saturday (AEDT) when it faces Sweden in Stockholm. It has also been drawn alongside Austria, Azerbaijan and Estonia in Group F.
Tedesco's men face Euro 2024 hosts Germany in a friendly on March 28.
