The NiCoCrAlYTa/10Ag/5Mo self-adaptive lubricating composite coating was designed and prepared by high velocity oxy-fuel (HVOF) spraying technology, and its hot corrosion and high-temperature tribological behaviors as well as the interaction mechanisms were investigated. A tremendous amount of β-Ag2MoO4 generated on the surface and acted as a lubricant film during friction when the composite coating was oxidized in no salt condition. The oxidizing process would be accelerated while the composite coating was exposed to molten salt mixtures. The boundaries between the reinforcement and matrix phases in the coating were firstly corroded and then produced NiO, Al2O3, Cr2O3 and the other porous oxides. And there was a continuous and protective rich-(Al, Cr) oxide scale on the surface of composite coating after molten 75Na2SO4 + 25NaCl and 75Na2SO4 + 20NaCl + 5V2O5 (wt%) salts corrosion. Besides, the mechanical and tribological properties of the corroded composite coating were improved. Compared to the case in molten Na2SO4-NaCl salt, the composite coating exposed to molten Na2SO4-NaCl-V2O5 salt was corroded more severely but had better mechanical properties and wear resistance.