One-step plasma electrolytic oxidation (PEO) process in a graphite-dispersed phosphate electrolyte was used to prepare a graphite-containing oxide composite coating on Ti6Al4V alloy. The composition and microstructure of the oxide coatings produced in the phosphate electrolytes with and without addition of graphite were analyzed by X-ray diffractometer (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The tribological properties of the uncoated Ti6Al4V alloy and oxide coatings were evaluated using a reciprocating ball-on-disk tribometer. Results showed that the graphite-containing oxide composite coating can be successfully produced on Ti6Al4V alloy in the graphite-dispersed phosphate electrolyte using PEO process. The graphite-containing oxide composite coating registered much lower friction coefficient and wear rate than the uncoated Ti6Al4V alloy and the oxide coating without graphite under dry sliding condition, exhibiting excellent self-lubricating property.