Titanium alloys have been widely used in aerospace and other fields due to their excellent properties such as light weight and high strength. However, the extremely poor tribological properties of titanium alloys limit their applications in certain special working conditions. In order to improve the tribological properties of titanium alloys, the zirconia coatings were prepared on the surface of a TC4 titanium alloy using the discharge plasma sintering method in this article. The influence of sintering parameters on properties such as density, adhesion, hardness, and phase composition, as well as tribological properties (friction coefficient, wear rate) were investigated, and the influence mechanism of the coating structure on its mechanical and frictional properties was analyzed. The results showed that, with the increase in sintering temperature, the density, bonding strength, and hardness of the zirconia coating were significantly improved. The zirconia coating prepared at a sintering temperature of 1500 °C and a sintering time of 20 min had the lowest friction coefficient and wear rate, which are 0.33 and 6.2 × 10 −8 cm 3·N −1·m −1, respectively. Numerical analysis showed that the increase in temperature and the extension of time contributed to the extension of the diffusion distance between zirconia and titanium, thereby improving the interfacial adhesion. The influence mechanism of different sintering temperatures and sintering times on the wear performance of zirconia coatings was explained through Hertz contact theory.