This paper examined the evolution of microstructure and its effect on the mechanical and tribological properties of ultralow friction Ti-doped diamondlike carbon (DLC) films, by adjusting the CH₄/Ar ratio under constant radio frequency discharge power and bias. The Raman, high resolution transmission electron microscopy, atomic force microscope and nanoindentation measurements consistently reveal or indicate the formation of curved graphene sheets or fullerenelike nanostructures with increasing CH₄/Ar ratio. The superior frictional performance (0.008–0.01) of Ti-DLC films can be attributed to the special microstructure related to the development of embedded fullerenelike nanostructures as a result of incorporation of TiO₂ clusters. The contributing factors include high hardness and cohesion, excellent toughness, high load-bearing capacity, as well as the ultralow shear resistance transform layer and the excellent antioxidation stability brought by the doped Ti.