This study experimentally investigated the effect of surface textures on the tribological mechanism of nitrided titanium alloy (Ti–6Al–4V). The titanium alloy samples were nitrided at various temperatures ranging from 750 to 950 °C for 10 h in a plasma nitriding furnace. Then, surface textures were fabricated on the polished titanium alloy and plasma nitrided samples by laser process system. The surface roughness, microhardness, and constitution of samples treated by single nitriding and samples treated by composite technology were characterized. The tribological properties of the samples were investigated on a CSM ball-on-disc tribometer. The results show that plasma nitriding effectively enhances the wear resistance of the substrate. The wear rate decreases first and then increases with the increase of nitriding temperature, and the wear rate reaches the minimum at 900 °C. However, the increase in roughness caused by nitriding treatment leads to an increase in the friction coefficient. It is found that surface textures can obviously reduce the friction coefficient of the nitrided titanium alloy. In addition, it can also reduce the wear rate of titanium alloys after nitriding at 900 and 950 °C. It can be concluded that the nitriding and surface texturing combined treatment can obviously reduce the friction coefficient and wear rate at the nitriding temperatures of 900 and 950 °C. This is attributed to the combined effect of high hardness of nitride layers and the function of micro-trap for wear debris of surface textures.