Due to the poor tribological properties, the applications of titanium alloy are restricted. Both laser texturing and surface coating are effective methods to enhance the tribological properties of titanium alloy surfaces. Hence, this study proposed a new ultrafast laser-induced simultaneous carbonization and texturization of titanium alloy surfaces to improve its tribological properties by modifying titanium alloy’s surface composition and micro-nanostructures in one step. A polymer film (polyimide, PI) was selected as the carbon source preplaced on the titanium alloy (Ti-6Al-4 V, TC4) surface. On the one hand, under ultrafast laser (picosecond 355 nm laser) irradiation, the laser-induced photothermal effect led to the carbonization of the polymer film and the formation of the pyrolytic carbon coating on the titanium alloy surface. Pyrolytic carbon also reacted with titanium alloy to form titanium carbides. On the other hand, ultrafast lasers also led to the melting and ablation of the titanium alloy surface, creating micro-nanostructures with interlocking micro-holes and micro-bumps. The coefficient of friction (COF) and wear rate of the titanium alloy surfaces were significantly reduced due to the synergistic effects of carbon coating and micro-nanostructures. It showed great significance in improving the tribological properties and the surface treatment of metallic materials.