Improving the tribological performance of titanium alloys is crucial to expanding their industrial applications. In this study, self-lubricating and wear-resistant coatings for TC4 alloy were achieved by combining plasma electrolytic oxidation (PEO) prepared using compounded electrolytes with incorporation of polytetrafluoroethylene (PTFE) as a solid lubricant. The investigation focused on the comprehensive effects of compounded electrolytes and PTFE on the microstructure and tribological behaviour of PEO coatings. After doping with PTFE, the coating prepared in electrolyte containing silicate, phosphate, and aluminate exhibited lowest wear rate (decreasing by 95.1%) and maximum hardness of 638.6 HV compared to other coatings. Additionally, the coefficient of friction (COF) significantly decreased from 0.8 to 0.16. This can be attributed to the strategy of depositing low-frictional discontinuous layers on hard PEO coatings.