The composition of the passive layers formed by electrochemical oxidation at different passivation potentials on Co-Cr-Mo and Co-Ni-Cr-Mo alloys in simulated physiological solution (SPS), with and without the complexing agent EDTA, was studied by X-ray photoelectron spectroscopy. Composition as a function of depth, cationic fraction and thickness of the passive film was determined. Chromium oxide is shown to be the major constituent of the passive layer on both Co-Cr-Mo and Co-Ni-Cr-Mo alloys. The minor constituents of the passive layers, Co- and Mo-oxide in the case of Co-Cr-Mo alloy and Ni-, Co- and Mo-oxides in the case of Co-Ni-Cr-Mo alloy, are also located in the outer part of the layer. EDTA affects the formation of the passive layer on each alloy. The content of Co-, Ni- and Mo-oxide in the passive layer is lower in the presence of EDTA, thus indicating increased solubility associated with higher stability constants for complexes of metal cations with EDTA.