To enhance the tribological performance of the conventional TiCrN coating, the MoSsub.2–TiCr coatings are deposited onto the TiCrN layer by magnetron sputtering. In general, the MoSsub.2 is implemented to enhance the friction reduction performance of the TiCrN coating, while the Ti and Cr are doped to increase the density of the structure and prevent MoSsub.2 from oxidizing. The results reveal that with an increase in the content of Ti and Cr in the MoSsub.2–TiCr top layer, the hardness and the coating–substrate adhesion force of the composite coating increase, respectively, due to the compact top layer. Further, the optimized Ti and Cr doping in the MoSsub.2 top layer greatly enhances the tribological properties of the TiCrN/MoSsub.2–TiCr composite coating with a friction coefficient as low as 0.06 and the wear rate is only 6% of the TiCrN coating. The main reason for the excellent tribological properties of the TiCrN/MoSsub.2–TiCr composite coating is probably due to the recrystallization of the MoSsub.2 in the process of wear.