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The 32-year-old was handed the armband by manager Roy Hodgson in the absence of regular skipper Joel Ward.
The Eagles were, however, below-par for much of the night, with Manchester United coasting to a comfortable 3-0 victory at Old Trafford.
First-half goals from Alejandro Garnacho and Casemiro were added to by a brilliant strike by Antony Martial in the second half.
Ayew, who has been one of Crystal Palace’s best players this season, captained the team and lasted the full 90 minutes.
The forward leads the charts for the most fouled player in the Premier League since the start of the 2022/23 campaign.
He has also started the current campaign in impressive fashion, having amassed three assists in the Premier League thus far, which won him Crystal Palace’s player of the month award for August.
Meanwhile, Ayew recently protested his overall rating of 74 on EA Sports’ recently launched FC 24 video game.
The famous game has been renamed following the conclusion of EA Sports’ partnership with world football governing body FIFA.
Players in the game have been rated in six categories – pace, shooting, passing, dribbling, defending and physical attributes.
The ratings of the Crystal Palace players were confirmed when they received their cards, with Eberechi Eze being the highest with a rating of 79.
Joachim Andersen, Cheick Doucouré, Marc Guéhi and Michael Olise follow suit with overall ratings of 78.
Ayew is further down the ratings, having been given an overall rating of 74 alongside teammates Will Hughes and Chris Richards.
Reacting to this, the Ghana international felt he had been cheated and jovially expressed his unhappiness with his rating in the game.
“What? no, 74 no chance. Nah nah nah I’m not having it anymore. How can I be the same as Hughesy [Will Hughes] and Chris Richards, nah. I’m not having it, I’m not having it,” the 32-year-old fumed when he received his card.