The Ghanaian striker scored a hat-trick in Monday's 4-0 friendly win against South Korea and will look to take that form into the tournament.
Ayew started on the bench but came on as a substitute in the sixth minute after Majeed Waris picked up a thigh injury, and he made the most of his opportunity in a convincing win for the Black Stars.
Asamoah Gyan added the other goal and Ghana will now hope to escape from the "Group of Death" and better their fantastic experience from South Africa four years ago where they reached the quarter-finals.
Jordan Ayew has been a target of West Brom's during the past two transfer windows and was likely to play a peripheral role but his performance last night will have forced him into manager Kwesi Appiah's plans.
He is experienced for such a young player and spent five seasons with Marseille before his loan spell at Sochaux at the end of the last campaign.
The pacey striker made quite an impact during his loan spell and netted five times in 17 appearances, and now looks ready to help Ghana enjoy another successful World Cup.
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Ayew also operates on both wings and is always involved around goal. He has scored five goals in 13 games for Ghana so far, including two in two games during qualification for the tournament.
The youngster plays in the national team with his brother Andre, who also plays with him at Marseille, and the pair will look to help the Black Stars get out of a very tricky group.
They open their campaign against the USA on Monday before playing Portugal and Germany, and with Jordan Ayew netting an impressive hat-trick against World Cup rivals South Korea last night, it is worth keeping an eye on how the 22-year-old performs in Brazil.