In this paper, MAO-Cu/Cu-(HEA)N composite coatings on TC4 titanium alloy were prepared by combining micro arc oxidation (MAO) with magnetron sputtering (MS) to enhance the wear resistance and antibacterial ability of the substrate in simulated seawater. The number of micropores on the surface of the composite coatings decreased with increasing CuSO4 concentration in the electrolyte, causing the surfaces to be flat and smooth. XPS and EDS analyses revealed that the MAO-Cu/Cu-(HEA)N composite coatings predominately contained TiO2, Cu2O, and (HEA)N. Moreover, the addition of CuSO4 increased the growth rate of the MAO coatings. Comparatively, the MAO-Cu/Cu-(HEA)N composite coating with 5 g/L CuSO4 showed superior wear resistance, reduced friction coefficient (approximately 0.2), and shallow and narrow grinding cracks were observed compared to the other coatings. Antibacterial experiments showed that the MAO-Cu/Cu-(HEA)N composite coatings had better bacterial killing effects than the TC4 substrate, which is of great significance to the antifouling abilities of titanium alloys in marine applications.