The experienced Serbian was unveiled during a press conference held at the GFA’s secretariat in Accra.
Rajevac will have two assistants - Maxwell Konadu and Borussia Dortmund assistant manager, Otto Addo, while Richard Kingson remains the team's goalkeeper's trainer.
He takes over from Charles Kwabla Akonnor, who was sacked following the Black Stars’ poor start to the 2022 FIFA World Cup qualifiers.
Rajevac, who managed Ghana from 2008 to 2010, has put pen to paper on a one-year deal, which would be automatically extended to February 2023 if he qualifies the team to the 2022 World Cup.
He had a successful spell with the Black Stars from 2008 to 2010 before he parted ways with the West African side.
The 67-year-old guided the team to the final of the 2010 Africa Cup of Nations (AFCON), where they lost narrowly to Egypt.
He also led Ghana to the quarter-finals of the World Cup in South Africa, making them only the third African nation to reach that far.
Since parting ways with Ghana in 2010, Rajevac has managed Al Ahli, Qatar, Algeria and last managed Thailand in 2019.
His immediate goal would be to help Ghana win next year’s Africa Cup of Nations (AFCON), as well as qualify for the World Cup in Qatar.
The Black Stars are paired with Comoros, Gabon and Morocco in Group G of the AFCON and boast three points from two matches in the World Cup qualifiers.
Rajevac will take charge of his first games in November when Ghana faces Zimbabwe in a double-header World Cup qualifier.
Meanwhile, the Serbian coach will earn a monthly salary of $30,000 and will get an additional bonus of $300,000 if he wins the AFCON and another $300,000 if the Black Stars qualify for the World Cup in Qatar.