CoCrMo orthopaedic alloy was oxidized potentiostatically in various simulated physiological solutions in order to reveal differences in the composition, thickness and structure of the surface layers formed as a function of solution composition. X-ray photoelectron spectroscopy, combined with angle-resolved measurements and depth profiling, was used for the purpose. The following simulated physiological solutions were used: (1) 0.9% NaCl, (2) simulated Hanks physiological solution containing various inorganic salts, (3) simulated Hanks physiological solution containing an aliquot of synovial fluid retrieved at a primary operation, and (4) minimum essential medium containing various inorganic salts, amino acids and vitamins. No significant differences between alloy treated in these solutions were observed after oxidation in the passive region: the oxide films are a few nanometres thick and, except in NaCl solution, contain a small amount of calcium phosphate. After oxidation at a potential in the transpassive range, however, the oxide thickness increases considerably due to incorporation of cobalt and molybdenum oxides. Further, the concentration of calcium phosphate increases. The layers formed in minimum essential medium and Hanks solution containing synovial fluid comprise nitrogen and carbon containing species. The addition of synovial fluid significantly affects the behaviour in Hanks solution. (C) 2012 Elsevier Ltd. All rights reserved.