Surface engineering is required to improve the poor lubrication performance of titanium alloys in many applications. In this study, an oxide coating with high-hardness was created on TC4 titanium alloy by using plasma electrolytic oxidation (PEO). The composition and structure of the PEO coatings were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman spectroscopy. The tribological properties of the PEO-treated TC4 were investigated in the presence of a polyalphaolefin (PAO) base oil with addition of molybdenum dialkyldithiocarbamate (MoDTC). The results show that the PEO-treated TC4 exhibits excellent lubrication performance in the presence of MoDTC. The oxide coating on the PEO-treated TC4 sample shows a tribo-induced catalysis effect enabling the decomposition of MoDTC to forms an effective lubricating film containing MoS2, resulting in reduced friction and wear.