De Bruyne will come in as a replacement for Eden Hazard.
Hazard announced his retirement from international football after Belgium's embarrassing group stage exit at the Qatar 2022 FIFA World Cup.
De Bruyne has won 97 caps and scored 25 goals since making his Belgium debut in 2010.
The 31-year-old Manchester City midfielder has featured in each of the last five major international tournaments for Belgium.
Real Madrid goalkeeper Thibaut Courtois and Chelsea's on-loan Inter Milan striker Romelu Lukaku have been appointed as the vice captains.
"It's an honour for me to be named and represent the country in this way," De Bruyne told RTL-TVI television after the announcement.
"I'm almost 32. I've never considered international retirement. I think I can still bring something to the table and help the youngsters."
De Bruyne will begin his tenure as Belgium captain against Sweden in a EURO 2024 qualifier.
Azerbaijan, Estonia and Austria are Belgium's other opponents in the group.
