Composition and structure of electrodeposited Fe-Pt-O films are investigated in dependence on deposition potential. At potentials positive to the hydrogen evolution, a solid solution of Pt with some Fe is present that can be explained by underpotential deposition of Fe. In the potential region where hydrogen evolution by proton reduction is a side reaction, oxygen is detected in the films. The 0 content scales with the Fe content and at least part of the Fe is oxidized. When applying more cathodic potentials, the fraction of Fe and 0 increases, grain size is reduced and an amorphous/nanocrystalline phase forms. The Fe content is pH dependent in this potential region. At even more cathodic potentials, overpotential deposition of Fe in the bcc structure sets in, the O content is reduced. The results are discussed with respect to thermodynamics in the Fe-Pt-(O) system. The concepts of underpotential deposition of Fe during Fe-Pt alloy deposition and of hydroxide formation due to a pH rise at the cathode are evaluated. These simple models can only partially describe the deposition process in agreement with the compositional and structural information obtained and a coupled mechanism is proposed. (c) 2006 Elsevier Ltd. All rights reserved.