The tribological behaviors of hydrogenated DLC film sliding against Al₂O₃, ZrO₂, Si₃N₄ and WC mating balls have been comparatively investigated by a ball-on-disk tribometer at 150 ℃ under helium and air (RH = 6%) conditions. The results showed that the mating material influenced the friction and wear behavior remarkably in helium atmosphere, where the wear rates were in inversely proportional to the friction coefficients (COF) of those tribo-pairs. Compared to the tests in helium, the tribological performance of DLC film significantly improved in air. Scanning electron microscope (SEM) and Raman spectroscopy were performed to study the friction behavior and wear mechanism of the film under different conditions. It suggested that the severe abrasion was caused by the strong interaction between the tribo-pairs in helium atmosphere at 150 ℃, whereas the sufficient passivation of the dangling bonds of carbon atoms at sliding interface by chemically active molecules, such as water and oxygen, dominated the ultralow friction under air condition. Meanwhile, Hertz analysis was used to further elucidate the frictional mechanism of DLC film under helium and air conditions. It showed that the coefficient of friction was consistent with the varied tendency of the contact radius, namely, higher friction coefficient corresponded to the larger contact radius, which was the same with the relationship between the wear rate and the contact pressure. All of the results made better understanding of the essential mechanism of hydrogenated DLC film sliding against different pairs, which were able to guide the further application of DLC film in the industrial fields of helium atmosphere.