The game was played to inaugurate the Congo's new Kintelle Stadium in Brazzaville.
The hosts were soon trailing to a Sagesse Babele own-goal in the 17th minute before Ghana doubled their lead two minutes later through Richmond Boakye.
Congo scored one back nine minutes after half-time through Babele and the score was level five minutes from time through substitute Hardy Bunguila.
In the end, it didn't prove enough as Villa's summer signing Ayew clinched the victory for the visitors in extra-time.
INTERNATIONAL REVIEW: Jordan Ayew scores winner in Ghana friendly. Full details here: http://t.co/DiYclhj3hH#AVFCpic.twitter.com/nBxpX9ZBac
— Aston Villa FC (@AVFCOfficial) September 2, 2015
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