He joins Egypt’s Ahmed Hassan and Cameroon’s Rigobert Song in the exclusive list of players to have achieved this feat.
The 34-year-old came on as a second-half substitute in the Black Stars’ disappointing defeat to Cape Verde in their opening game of the 2023 AFCON on Sunday.
A lacklustre performance saw the Black Stars fall behind after just 17 minutes following Jamiro Monteiro's rebound.
Ghana bounced back in the second half through Alexandre Djiku’s header and, for a moment, it looked like the night could belong to them.
However, Cape Verde stunned them late in the game, with Garry Rodrigues taking advantage of a defensive mix-up to score the winner.
Ayew, however, came on to chalk a piece of history when he replaced Ranford Yeboah Konigsdoffer in the 62nd minute of the game.
The Le Havre man is now the joint record holder for playing in the most AFCON tournaments, alongside Hassan and Song.
The Black Stars skipper is also just one more appearance away from equaling Song’s record of 36 appearances in the AFCON.
Ayew recently revealed his ambition to break every record in sight, saying: “I think there are two or three records to be broken. I will be happy to achieve that but the most important thing is the team and not my personal achievement.
“Breaking records and not winning or not having the results as a team is not my ambition as the captain of the team. I want to do everything possible to break the record but most importantly, I want to win games as the leader of the team,” he added.