Laser cladding of the TiAl/Fe+Co-coated WC+TiB2 pre-placed mixed powders on a Ti-6Al-4V alloy substrate can be used to form TiB2/α-W2C-reinforced composite coating, which improved the wear resistance of the substrate. To further improve the TiB2/α-W2C-reinforced composite coating, yttria partially stabilized zirconia (YPSZ) was added into the pre-placed powders. A metallurgical bonding was formed between the YPSZ-infused composite coating and the substrate. Many amorphous alloys were produced in this composite coating due to the action of YPSZ, and such coating showed fine microstructure. Thus, it is feasible to further improve the wear resistance of the laser clad TiB2/α-W2C-reinforced composite coating through the addition of YPSZ.