The potential of lower friction and desired wear for nickel-based composite coating system at high temperatures was explored, where multiple oxides were incorporated into nickel matrix during the atmospheric plasma spraying process. The phase composition and microstructure of wear track were characterized by XRD, Raman, SEM/EDS, and FIB/STEM. The further addition of MoO3 allows for an effective reduction of friction coefficient at 800 degrees C. The surficial and interfacial analysis well confirmed that a protective tribo-layer presenting on the contacting surface, in which binary oxides (A-TiO2, R-TiO2, ZnO, NiO), molybdates and titanates (ZnMoO4, NiMoO4, and Zn2TiO4) were identifiable. The association of friction and wear properties with interface chemistry was discussed for the nickel-based coatings with the addition of multiple oxides (TiO2-ZnO-MoO3).