To reduce the internal stress and obtain thicker DLC film, a multilayer structure DLC comprised of Ti-doped nanolayer were deposited on Titanium alloy substrate by pulse cathodic arc technology, the Ti content is decreased from bottom to top layer. And the surface layer is carbon deposited with ion–assist deposition. The chemical composition of the films was determined using X-ray photoelectron spectroscopy (XPS). The film structure was characterized by Raman spectroscopy. Other properties of the films are evaluated by Dektak 8 Stylus Profilometer, nano-hardness tester and reciprocating sliding wear tester. And the thickness, hardness, and friction coefficient of two samples are 2.2μm, 1.5μm, 5200Hv, 5500Hv, and 0.09, respectively. The internal stress, calculated by Stoney’s equation, is 2.2GPa, 2.1GPa. And the adhesion strength is 40N/mm2, 35N/mm2.