To address the challenges related to poor wear resistance, high friction coefficient, inadequate grinding performance, and low hardness of TC4 titanium alloy, this study aims to enhance its applicability. Composite coatings were fabricated on TC4 substrate using varying proportions of Ni60 powder and Ni/MoS2 powder. The impact of different powder ratios on coating quality was assessed through analyses of coating morphology, microhardness, and friction reduction performance. Experiments show that the macroscopic morphology of the prepared composite coating is well formed, but its cross-sectional morphology changes from gentle to excessive to convex at the junction of the cladding layer and the substrate with the increase of Ni/MoS2 content, and defects such as porosity and cracks appear. Coating microhardness and Ni/MoS2 addition is positive correlation, friction coefficient and Ni/MoS2 addition of the first decline and then rise trend, comprehensive comparison, when the addition of Ni/MoS2 mass fraction of 0.2 can obtain a more excellent composite coating, the microhardness of the coating can reach 950—1 000 HV, about 2.8 times the TC4 substrate, and the coating friction coefficient is reduced to 1/3 of the friction coefficient of TC4 substrate. These findings demonstrate that the proposed experimental approach effectively mitigates the low hardness and poor wear resistance issues of TC4 titanium alloy in practical applications.