The honour is bestowed on political leaders of the Frontline States who provided solidarity and unity in supporting the liberation war in Zimbabwe in the 1970s.
Apart from Khama, Mugabe also conferred the honour on Dr Kenneth Kaunda, Zambia's founding father. The same accolade was posthumously given to founding fathers Agostinho Neto of Angola, Samora Machel of Mozambique and Julius Nyerere of Tanzania.
Several more people deemed to have "distinguished themselves in different fields and service to the liberation of Zimbabwe and its general post-independence socio-economic development" were conferred with other honours and awards.
A citation described Khama as a nationalist, pan Africanist, scholar, former head of state and knight while the late Neto was described as a gallant soldier, politician and poet.
Nyerere was described as one of the founder members of the Organisation of African Unity (now African Union), founding father of the union between Tanganyika and Zanzibar, philosopher, educationist, playwright and liberation fighter.
Machel's citation said he was a revolutionary, statesman and poet while Kaunda is a nationalist, freedom fighter and HIV/AIDS activist.
Zimbabweans who were honoured include the late veteran nationalists and icons of the liberation struggle against Britain, Joshua Nkomo, Simon Muzenda and Samuel Parirenyatwa. Nkomo and Muzenda are former vice-presidents to Mugabe and were awarded posthumously the Order of the Great Zimbabwe (Gold).
Parirenyatwa was Zimbabwe's first black medical doctor.
Munhumutapa is the founding father of the great empire, which existed south of the Zambezi River during the pre-colonial era. His kingdom covered most of present day SADC region.
"Sir Seretse Khama will be given the award in recognition of his exceptional commitment to the eradication of colonial domination, unyielding dedication to Pan Africanist ideas and sterling contribution to Zimbabwe's liberation struggle and the pursuit of justice and equality," said a statement from the department of information and publicity in Mugabe,s office.