In order to improve the resistance of titanium alloy on the tribological characteristics, laser processing was used to build grid and dot micro-structure with spacing of 100μm and 300μm on Ti6Al4V alloy surface. The Nano-SiO2 powders were coated on the micro-structures to build micro-nano structures. The contact angles and roll angles were measured by contact angle measurement. The micrograph and wear tracks were investigated by LEXT OLS4000 3D microscope. Tribological performance were evaluated by CETR Universal Micro-Tribometer(UMT). The results show that the micro structure surface is in hydrophobic state that is in accordance with Wenzel model, while the surfaces with the micro-nano structure formed by coating the Nano-SiO2 is in super hydrophobic state that is in accordance with Cassie model. With the increase of spacing, the surface is more easily to be wet. The dot surface is more easily to be wet than grid surface. When the load is 50 mN, friction-reducing and wear protection of the surface enhance with weaken of surface wettability. When the load is 5 N, coating SiO2 can enhance wear resistance and friction-reducing of the surface significantly, while wear resistance of the gird surface is stronger than that of the dot.