The centre-back is expected to be handed the captaincy by Black Stars coach Kwesi Appiah in the upcoming world cup qualifier.
The 27-year-old has made over 50 appearances for the Black Stars since making his debut in 2009, and is now one of the senior-most players currently in camp.
The Black Stars are currently without a number of key players for the Congo clash, including Asamoah Gyan and Andre Ayew.
The Black Stars captain and his deputy have both been ruled out of the encounter due to groin and thigh injuries respectively.
Coach Kwesi Appiah is therefore set to task Mensah with leadership duties on Tuesday, as Ghana fights to keep their slim hope of qualification to the 2018 world cup.
Influential right-back Afful Harrison, as well as Jordan Ayew are also set to miss the clash, with midfielder Ebenezer Ofori also a major doubt after being robbed at gun point barely 24 hours to the Congo clash.
Ghana will face Congo at lunch time on Tuesday at the Stade Kintele stadium in Brazzaville.