Titanium alloys have broad application potential across various fields due to their excellent comprehensive properties. However, their poor wear resistance limits their applications. Flower-like spherical solid lubricants show promise as effective lubricant additives for reducing friction and wear. In this study, layered double hydroxides (LDH) microspheres, assembled from nanosheets, were synthesized. Additionally, a textured surface was created on the titanium alloy using ultraviolet laser micro-machining technology. The tribological performance and anti-wear mechanisms of the surfactant-functionalized LDH (C-LDH) as an additive in oil at different concentrations were investigated. The synergistic effect of the textured surface and C-LDH significantly reduced the friction coefficient (COF) of TC4 alloy. Compared to pure oil, lubrication with oil containing 2.5 wt% C-LDH reduced the COF by 68.75%, and compared with dry friction, the COF decreased by 88.09%. These improvements are attributed to the superior lubricating performance of C-LDH, resulting from its layered structure and the formation of a tribofilm during friction. Furthermore, the micro-grooves on the textured surface provided a reservoir effect, contributing to “self-compensating lubrication” and assisting in wear debris collection. In conclusion, a synergistic protective strategy combining the textured surface and LDH was developed, offering effective protection for TC4 alloys. This work presents a novel lubricant additives and provides valuable insights into improving the tribological performance of titanium alloys.