Improving the fracture toughness and wear resistance of Cr2O3 coating is of great significance for its application in high-end fields. Incorporating TiO2 is an effective toughening strategy, yet its effect on wear resistance is contradictory. In this work, the effects of TiO2 content on the microstructure, mechanical properties, and tribological properties of the plasma-sprayed Cr2O3–xTiO2 composite coatings were studied. The results demonstrate that the microstructure of the composite coatings only contains the Cr2O3 and TiO2 phases without an intermediate phase. The composite coatings exhibit lower porosity, higher fracture toughness, and better wear resistance compared to pure Cr2O3 coating. With the increase of TiO2 content, the fracture toughness and wear resistance of composite coatings exhibit an initial increase followed by a decrease. The Cr2O3–15TiO2 composite coating presents the highest fracture toughness of 6.53 MPa m1/2 and the lowest wear rate of 0.82 × 10−6 mm3/(N m). The improvement in fracture toughness of the composite coatings is due to the reduction of porosity, crack deflection, and branching by TiO2. Furthermore, the wear mechanism shifts from brittle fracture, fatigue wear, and oxidative wear in pure Cr2O3 to oxidative wear in the composite coatings. This is attributed to the enhanced toughness of composite coatings via TiO2, reducing the crack initiation and spalling. This work provides theoretical guidance and technical support for the performance optimization of the Cr2O3 coating.