The WSi_2/W_5Si_3 composite coating was prepared on the surface of the TC4 titanium alloy by magnetron sputtering( PVD),chemical vapor deposition( CVD) and thermal diffusion siliconizing method. The X-ray diffractometer,scanning electron microscope and energy spectrometer were used to analyze the structure,morphology and microdomain chemical composition of the composite coating. The microhardness,adhesion and wear resistance of the composite coating were tested. The results show that the thickness of the WSi_2 layer and W_5Si_3 layer of the WSi_2/W_5Si_3 composite coating is 20 μm and 56 μm,and the average microhardness is 10. 70 GPa and 8. 32 GPa respectively. The bonding force between WSi_2/W_5Si_3 composite coating in substrate is 171. 6 N. The surface friction factor of the WSi_2/W_5Si_3 composite coating is 0. 75,and the wear rate is 1. 184 × 10-6 mm3·mm-1. The WSi_2/W_5Si_3 composite coating prepared on the surface of TC4 titanium alloy has a uniform and dense structure,and it is well combined with the substrate.