Coatings with a thickness from ~40 to ~50 µm on Ti6Al4V titanium alloys were formed by plasma electrolytic oxidation (PEO) in a silicate-hypophosphite electrolyte with the addition of graphene oxide. The PEO treatment was carried out in the anode–cathode mode (50 Hz) at a ratio of anode and cathode currents of 1:1; their sum density was 20 A/dm2, and the treatment’s duration was 30 min. The effect of the graphene oxide’s concentration in the electrolyte on the thickness, roughness, hardness, surface morphology, structure, composition, and tribological characteristics of the PEO coatings was studied. Wear experiments, under dry conditions, were carried out in a ball-on-disk tribotester with an applied load of 5 N, a sliding speed of 0.1 m·s−1, and a sliding distance of 1000 m. According to the obtained results, the addition of graphene oxide (GO) into the base silicate-hypophosphite electrolyte leads to a slight decrease in the coefficient of friction (from 0.73 to 0.69) and a reduction in the wear rate by more than 1.5 times (from 8.04 to 5.2 mm3/N·m), with an increase in the GO’s concentration from 0 to 0.5 kg/m3, respectively. This occurs due to the formation of a GO-containing lubricating tribolayer upon contact with the coating of the counter-body in the friction pair. Delamination of the coatings during wear occurs due to contact fatigue; with an increase in the concentration of GO in the electrolyte from 0 to 0.5 kg/m3, this process slows down by more than four times.