A systematic study of the atomic and electronic structure of the γ-TiAl(111)/α-Al2O3(0001) interface with intermediate metal (Nb, Mo, Ni, Re) and oxide (Nb2O5, MoO3) layers has been performed by the projector augmented-wave method within density functional theory. The work of separation at the interfaces in dependence on the cleavage plane has been calculated. It is shown that a high adhesion energy obtained at the interface with the O-terminated α-Al2O3 is decreased at the γ-TiAl/Me interface but it remains enough high at the Me/α-Al2O3(0001)O interface due to a large ionic contribution to the chemical bonding. The influence of formation of intermediate impurity oxide layers on the adhesive properties of the alloy/oxide interface is discussed as well. The obtained results indicate that the fracture will occur inside the impurity oxide or its interface with the alloy.