In aerospace, some moving parts will meet with simultaneous high temperature and vacuum environments. In this study, the tribological behavior of a nickel alloy matrix solid lubricant composite was contrastively investigated under both air and vacuum conditions from room temperature to 800 °C. Results showed that both the friction coefficient and the wear rate of the composite were highly dependent on testing temperature and atmosphere. The friction coefficient in vacuum was lower than that in ambient air. The compositions of the frictional surfaces were analyzed, based on which, the mechanism of friction and wear was proposed.