This article reports the results of a study of the formation of phosphate films formed directly on the surface of metallic copper without the presence of an oxide layer. The experiments were performed using aqueous electrochemical treatment in an anaerobic electrochemical cell designed to allow an oxide-free metal surface to be exposed to electrochemical treatment without having to expose the electrode to the atmosphere. The electrochemical treatment was performed using negative voltages (versus a saturated calomel electrode) in 5 M orthophosphoric acid. When the experiments were performed outside the anaerobic cell with as-received metallic copper, the treatment leads to the removal of oxide to leave a metallic surface with negligible amounts of oxide. In the anaerobic cell, however, a film consisting of a mixture of Cu(I) metalphosphate and orthophosphate is formed directly bonded to the metal. When this film is exposed to air for ten days, the surface film, still directly bonded to the metal, is oxidized to Cu(II) orthophosphate, this film remaining in a stable condition. The surface chemistries were identified by valence-band photoemission interpreted by cluster calculations. The work illustrates how, by starting with an oxide-free metal surface and performing the treatment in an inert environment in an anaerobic electrochemical cell, one can achieve unusual surface chemistries.