Bulk Ti3AlC2 was prepared via hot pressing TiC, Ti and Al powders in vacuum. The sliding wear of Ti3AlC2 against Al2O3 at room temperature up to 800°C was investigated on a SRV-IV oscillating friction and wear tester. Reduced wear and wear transition of Ti3AlC2/Al2O3 tribo-couple were found by increasing temperature. The worn surfaces of both Ti3AlC2 and Al2O3 were analyzed by scanning electron microscope and X-ray photoelectron spectrometer. It was found that the severe wear of Ti3AlC2 and Al2O3 from room temperature to 200°C was related to mechanical wear, i.e. grain fracture and pullout of Ti3AlC2. At temperature higher than 400°C, the tribo-oxidation layer on the worn surface of Ti3AlC2 containing TiO2 and Al2O3 was beneficial for reducing wear of both Ti3AlC2 and Al2O3.