The Cr2O3 ceramic films prepared by multi-arc ion plating possess a low friction coefficient, good wear resistant and oxidation resistance. Meanwhile, high temperature annealing could improve the mechanical properties of Cr2O3 films significantly. In previous work, we found that the metal elements in the substrate would diffuse to the film surface and oxidize to form a ternary metal oxide with lubricating property. Thus, in order to research the diffusion behaviours of the metal elements in the substrate, the effects of microstructure evolution of the substrates on the metal elements diffusion in high temperature, and the evolutions of morphologies, microstructure and tribological properties of the Cr2O3 films were also researched in detail.