Precision glass molding (PGM) is an efficient process used for batch manufacturing of high-precision glass optical elements. In this process, nickel phosphide (Ni–P) alloy is commonly utilized as a mold material due to its superior turning properties. However, the Ni–P mold suffers from issues such as diffusion of phosphorus elements, poor wear resistance, and easy peeling of the DLC coating during molding. To address these problems, the current study proposes enhancing the molding performance of mold by depositing a composite coating layer of Ti/Ti-DLC onto the surface of Ni–P using the filtered cathodic vacuum arc technology (FCVA). The effects of different flow rates of C2H2 on Ti-DLC coatings were analyzed in terms of composition, microstructure, mechanical, tribological, and molding properties. The results revealed that as the C2H2 flow rate increased, the Ti content of coatings decreased from 13.56 to 2.17 at.%. Additionally, the film microstructure transformed from TiC polycrystalline composite films to nanocrystalline amorphous composite films and finally to amorphous films. The Ti-DLC coatings with a nanocrystalline composite structure exhibited excellent overall performance when Ti content is 7.75 at.%. These coatings are suitable as protective coatings for microstructured array mold and demonstrate good stability at a molding temperature of 500 °C.