Kaba Diawara and Mandjou Diallo will replace Didier Six in charge of Guinea for the country's final two World Cup qualifiers next month.
The Syli National are unable to reach next year's tournament in Qatar after taking just three points from their first four matches in Group I of African qualifying.
The Guinean Football Federation (Feguifoot) said negotiations with Six over an "amicable separation" were under way in a statement on its website.
Earlier this month, Guinea were forced to play two of their home qualifying matches on away soil following a coup in the country.
Diallo will be assistant to Diawara, who has no previous experience as a senior head coach.
Diarawa, 45, had spells at Toulon, Bordeaux, Arsenal, Marseille and Paris St-Germain during his playing career, while also representing Guinea.
Former France international Six, 67, has been in charge of Guinea since September 2019 and guided the west Africans to qualification for next year's Africa Cup of Nations.
Guinea have been drawn in alongside Senegal, Zimbabwe and Malawi in Group B for the tournament in Cameroon, which begins on 9 January.
Six previously led Togo to the Nations Cup quarter-finals in 2013.