In this paper, a magnetron sputtered nano-structured multilayer coating TiAlN/VN, grown on hardened tool steel substrate, has been investigated in un-lubricated ball-on-disk sliding tests against an alumina counterface, to study the friction and wear behaviours at a broad range of testing temperatures from 25 to 700 0 C, followed by comprehensive analysis of the worn samples . The associated wear mechanism changed to severe wear dominated by cracking and spalling. From 500 0 C and so on, accelerated oxidation of the TiAlN/VN became the controlling process. This led first to the massive generation of oxide debris and maximum friction of µ = 1.1 at 500 0 C, and then to fast deterioration of the coating despite the lowest friction coefficient of µ < 0.3 at 700 0 C.