Ayew took advantage of some woeful marking by Burkina Faso to head home after half-an-hour and qualify in second place from Group B, behind Ivory Coast.
Burkina Faso's hopes of staging a comeback suffered a setback with the 66th-minute dismissal of defender Mamadou Tall.
However, it was a stuttering display by the Black Stars whose injury problems entering the match had worsened after Chelsea's Michael Essien was ruled out of the tournament.
Burkina Faso needed only to draw after holding Ivory Coast in the first match but Ghana had to win following their defeat to the Elephants.
Milovan Rajevac's side had no option to attack from the outset and they won a free-kick on the left wing in the first minute but Asamoah Gyan sent the ball over the bar.
The Ghanaians were then grateful to their goalkeeper in the eighth minute after the pacy Jonathan Pitroipa left defenders in his wake as he bore down on goal but Richard Kingson came out and blocked the shot from a tight angle.
Ghana then took the lead through Ayew's header. A free-kick cleared to the right was sent back into the box finding Ayew unmarked, and the midfielder diverted his header downwards into the right-hand corner of the net.
Ghana almost doubled their lead when Haminu Draman sent a ball across goal with Gyan just failing to get a touch.
The Burkinabe then sent in a teasing delivery from the right which narrowly eluded a lunging Bakary Kone with Kingson rooted to his goal line and Kone then blazed a shot over the top when well-placed.
However, just as the Burkinabe appeared to be making inroads, they were reduced to ten men after Tall was sent off following a challenge which left Gyan clutching his face, although the decision appear a harsh one.
Draman then missed a clear chance to double Ghana's lead when he put the ball into the side netting from close range when unmarked before Samuel Inkoom also went close.
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