The potential for the use of copper coatings on steel switching mechanisms is abundant owing to the high conductivities and corrosion resistance that they impart on the engineered assemblies. However, applications of these coatings on such moving parts are limited due to their poor tribological properties; tendencies to generate high friction and susceptibility to degradative wear. In this study, we have fabricated a fluorinated graphene oxide-copper metal matrix composite (FGO-CMMC) on an AISI 52100 bearing steel substrate by a simple electrodeposition process in water. The FGO-CMMC coatings exhibited excellent lubrication performance under pin-on-disk (PoD) tribological sliding at 1N load, which reduced CoF by 63 and 69%, compared to the GO-CMMC and pure copper coatings that were also prepared. Furthermore, FGO-CMMC achieved low friction and low wear at higher sliding loads. The lubrication enhancement of the FGO-CMMCs is attributed to the tribochemical reaction of FGO with the AISI 52100 steel counterface initiated by the sliding load. The formation of an asymmetric tribofilm structure on the sliding track is critical; the performance of the FGO/Cu tribofilm formed in the track is boosted by the continued fluorination of the counterface surface during PoD sliding, passivating the tribosystem from adhesion-driven breakdown. The FGO-CMMC and GO-CMMC coatings also provide increased corrosion protection reaching 94.2 and 91.6% compared to the bare steel substrate, allowing for the preservation of the long-term low-friction performance of the coating. Other influences include the improved interlaminar shear strength of the FGO-containing composite. The excellent lubrication performance of the copper matrix composite coatings facilitated by FGO incorporation makes it a promising solid lubricant candidate for use in mechanical engineering applications.