One-step forming TiCp/Ni3Al-Ni3Al multi-coating on powder metallurgy 316L stainless steel substrate was fabricated by vacuum hot-pressing sintering technology and its wear performances at different loads and ambient temperatures were investigated. The wear weight loss of TiCp/Ni3Al-Ni3Al multi-coating increased with the increase in the applied load and a mild-to-severe wear transition occurred. Inversely, the coating’s wear weight loss decreased as the ambient temperature increased. The high wear resistance at elevated temperatures was mainly attributed to high work-hardening capacity and high temperature strength of Ni3Al matrix. Besides, the mechanically mixed layer with dispersed TiC particulates prevented the substrate from plastic deformation and thermal softening, which were conducive to improve the wear resistance of the coating.