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The Black Stars looked set to come away with a draw after Alexander Djiku headed home to cancel out a Jamiro Monteiro goal for Cape Verde at the Felix Houphouet Boigny Stadium in Abidjan.
Majeed Ashimeru was also denied a goal for Ghana following a lengthy VAR check, but Cape Verde grabbed three points in the Group B match as Rodrigues found the net at the death.
It was a fine victory for the island nation, who reached the knockout stage at the last AFCON, and puts them top of the section after group rivals Egypt and Mozambique drew 2-2 earlier.
The evening was also notable for the second-half appearance as a substitute of Andre Ayew, with the 34-year-old becoming only the third player to feature in eight editions of the competition.
He now shares the record with Rigobert Song, currently coach of Cameroon, and Egyptian Ahmed Hassan.
