TiAlN/VN multilayer coatings exhibit excellent dry sliding wear resistance and low friction coefficient, reported to be associated with the formation of self-lubricating V2O5. To investigate this hypothesis, dry sliding ball-on-disc wear tests of TiAlN/VN coatings on flat stainless steel substrates were undertaken against Al2O3 at 25 0 C, 300 0 C and 635 0 C in air. The coating exhibited increased wear rate with temperature. The friction coefficient was 0.53 at 25 0 C, which increased to 1.03 at 300 0 C and decreased to 0.46 at 635 0 C. Detailed investigation of the worn surfaces was undertaken using site-specific transmission electron microscopy (TEM) via focused ion beam (FIB) microscopy, along with Fourier transform infrared (FTIR) and Raman spectroscopy. Microstructure and triboinduced chemical reactions at these temperatures were correlated with the coating's wear and friction behaviour. The friction behaviour at room temperature is attributed to the presence of a thin hydrated tribofilm and the presence of V2O5 at high temperature.