Abstract Titanium alloys have excellent mechanical properties, but poor tribological properties limit their application as dynamic friction components. Micro‐arc oxidation (MAO) is a technique to generate a ceramic layer on the metal surface to obtain better wear resistance, but the structure of the ceramic layer leads to a high coefficient of friction. In this study, MAO–MoS 2 composite coatings were prepared on the surface of titanium alloy (TC6) by a combination of MAO and hydrothermal reaction. The tribological performance of the composite coatings was investigated by a ball‐on‐disk high‐temperature tribometer under room temperature to 300°C, and the corresponding lubrication mechanism was revealed. The results show that the average friction coefficient of the composite coating is reduced by 89.1% and the wear rate is reduced by 91.4% compared to the pure TC6 at 300°C, which is attributed to the introduction of the MAO ceramic layer and MoS 2 lubrication element synergistically improves the friction reduction and wear resistance of TC6. The findings of this study are expected to expand the engineering applications of titanium alloy components in aerospace and other related fields.