A composite layer was prepared on the Ti-6Al-4V alloy surface by ion nitriding, magnetron sputtering Mo and ion sulfurizing composite treatment technique. The phase structure, morphology, and cross-sectional element distribution of composite layer were analyzed. Friction and wear properties of composite layer were tested by MM-200 laboratory tester. XRD analysis showed that the composite layer was mainly comprised of Ti, Mo, MoS2, TiN, and transition layer. This composite layer is perfect wear-resistant surface due to existence of self-lubricating MoS2 on hard Mo and TiN layers with good anti-friction ability. Thereby, the results of friction and wear test showed that anti-wear performance of Ti-6Al-4V alloy after composite treatment was remarkably improved under dry and sliding conditions. Both the friction coefficient and the wear loss of the nitriding-Mo plating-sulfurizing layers were lower than that of the nitriding layer due to the formation of the MoS2 layer on Mo and TiN layers.