Abstract: Due to the processing conditions of high speed steel (HSS) work rolls is harsh (high temperature, high stress, relative sliding with rolled material, and other special working conditions), the work roll will inevitably suffer oxidation, wear and tear. The oxide film may influence the tribological properties and vice versa. Accordingly, investigating the oxidation and tribological behaviors of HSS roll materials at high temperature and elucidating the oxidation kinetics, the wear mechanism, and the mechanism of friction reduction and anti-wear of roll materials and counterparts will be helpful to reduce wear and increase the life of roll materials, improve the quality of rolled materials, and heighten the production efficiency. In this paper, the high temperature oxidation (isothermal oxidation and cyclic oxidation) and friction experiment of one kind of HSS samples were carried out at 600 ℃, and the oxidation kinetics, the microstructure on oxidation surface and cross-section were analyzed, as well as the wear mechanism were explored. The original HSS sample mainly contains Fe-based solid solution and carbides (VC, Cr₇C₃ and Mo₂C). Although the cyclic oxidation rate was much larger than the isothermal oxidation rate, the oxidation kinetics under both conditions conform to the parabolic law, indicating that the oxidation was controlled by the ion diffusion process. The products were mainly Fe₂O₃ and V₂O₅ for isothermal oxidation, while Fe₃O₄ and CaCO₃ dominated the cyclic oxidation, no V₂O₅ could be detected during cyclic oxidation. Few Cr₇C₃ and Mo₂C carbides were oxidized due to the better oxidation resistance. With the proceeding of the cyclic oxidation, the CaCO₃ segregate at grain boundary firstly and then cover the surface. During cyclic oxidation, due to the difference of thermal conductivity between matrix and carbide, the cracks initiated and propagated at carbides. The presences of CaCO₃ and cracks facilitated the inward diffusion of oxygen, thus speeds up the oxidation. Under cyclic oxidation, the oxide film was thicker, and the bonding strength between the oxide film and the substrate was higher. However, due to the presence of CaCO₃ and cracks, prolonging the cycle oxidation time may have caused premature destruction of the oxide film. The friction coefficient leveled off and stabilized at about 0.47 after a short running-in, and the wear rate of HSS pin and counterpart Q235 steel disk was low and even negative wear 1.855×10⁻⁷ g/(N·m) and −1.496×10⁻⁷ cm³/(N·m), respectively. The wear products of HSS pin were similar with the isothermal oxidation, with the iron oxide (Fe₃O₄ and Fe₂O₃), Fe matrix, vanadium oxide (V₂O₅) and carbides can be observed. Compared to the Fe₂O₃ main phase after isothermal oxidation, the dominant products were Fe₃O₄ after wear, which was contributed to the less oxygen partial pressure during the wear test. The grooves, spalling pit, wear debris existed on the wear surface of HSS pin, indicating the wear mechanisms of pin are mainly oxidative, abrasive and adhesive wear. For the counterpart disc, the wear products are Fe₂O₃, Fe₃O₄, V₂O₅, Fe matrix and carbide, which was same with the pin. On the wear surface of Q235 disc, the oxidation zones, wear debris zones and tribolayer containing V and Cr could be observed. Because the Q235 is free of V, Cr, Mo, the detected V, Cr, Mo element should come from the pin. The presence of tribolayer proves the occurrence of material transfer, and the tribolayer could separate the direct contact of the HSS pin and Q235 disc, which was beneficial for reducing the friction coefficient and wear rate. The material transfer was responsible for the negative wear of the counterpart disc, also may account for the reduction of rolled material quality. The wear mechanism of the Q235 counterpart disc was oxidative and adhesive wear.