A hydrogenated amorphous carbon (a-C:H) film shows an ultralow friction coefficient (COF, lower than 0.01); however, its wear life is short in vacuum, and the mechanisms are still not well-understood. This study demonstrates the vacuum tribological behaviors of the a-C:H film can be regulated by interfacial activity. The strong interfacial activity induced continuous transfer of carbon from the film to counterface, causing the formation of a porous transfer film and severe wear of the a-C:H film. Interestingly, weak interfacial activity is beneficial to form spherical-like carbon at the sliding interface, which shields the interaction of dangling bonds and contributes to lower COF and wear of film. Notably, the catalytic nature of Au induced perfect graphene nanoscrolls around Au nanoparticles at the sliding interface, achieving ultralong vacuum wear life. This Letter unifies the understanding of vacuum tribological properties of a-C:H film and provides new insight for prolonging the life of carbon films in vacuum.