Artificial hip joints operate in aqueous biofluids that are highly reactive towards metallic surfaces. The reactivity at the metal interface is enhanced by mechanical interaction due to friction, which can change the near-surface structure of the metal and surface chemistry. There are now several reports in the literature about the in-situ generation of reaction films and tribo-metallurgical transformations on metal-on-metal hip joints. This paper summarizes current knowledge and provides a mechanistic interpretation of the surface chemical and metallurgical phenomena. Basic concepts of corrosion and wear are illustrated and used to interpret available literature on in-vitro and in-vivo studies of metal-on-metal hip joints. Based on this review, three forms of tribomaterial, characterized by different combinations of oxide films and organic layers, can be determined. It is shown that the generation of these tribofilms can be related to specific electrochemical and mechanical phenomena in the metal interface. It is suggested that the generation of this surface reaction layer constitutes a way to minimize (mechanical) wear of MoM hip implants.