In order to improve the tribological properties of NiAl intermetallic, Ag₃VO₄ nanoparticles with a size of 100–200 nm were synthesized by hydrothermal method and NiAl/Ag₃VO₄ composites were successfully prepared by mechanical alloying and sintering technique. The composition and microstructure of milled powders and sintered composites were characterized and the tribological properties were evaluated. The results showed that NiAl-based composites were consisted of B2 ordered NiAl matrix and metallic Ag/vanadium oxide precipitates, which were formed by the decomposition of silver vanadate. Wear testing results indicated that NiAl-based composites containing silver vanadate exhibited superior tribological properties at elevated temperatures. Subsequently, Raman results demonstrated that the reproduction of silver vanadate was responsible for the improvement of tribological properties at elevated temperatures.