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Aspects of the structural and electronic properties of hydrous oxide films of Ni and of composite (9: 1) NUCo and (9:l) Ni/Fe, prepared by electrodeposition, have been examined in alkaline electrolytes using in situ X-ray absorption fine structure (XAFS). An analysis of the X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) for the Co and Fe K-edges of these composite hydrous oxides revealed that, regardless of the oxidation state of nickel sites in the films, the guest metal ions are present as Co3+ and Fe3+ and that the cobalt-oxygen distance d(Co-0) = 1.90 f 0.02 8, and d(Fe-0) = 1.92 f 0.02 A. The latter values are in excellent agreement with d(Me-0) (Me = Co or Fe) in CoOOH and p-and y-FeOOH, respectively, determined by conventional X-ray diffraction. Two clearly defined Me-Ni first coordination shells could be observed in the Fourier transforms (FT) of the K-edge EXAFS of the guest metal recorded at a potential at which both NiZ+ and Ni3+ sites are expected to be present. The relative intensities of these F T features could be varied by changing the applied potential or, equivalently, the relative population of the two nickel sites. On the basis of these results, the Me-Ni shells are ascribed to Co3+ adjacent to Ni2+ and Ni3+ sites. Furthermore, d(Ni-Co) and d(Ni-Fe) for a given nickel oxidation state are found to be essentially the same as those observed for d(Ni-Ni) in pure nickel hydrous oxide films. This provides evidence that Co3+ and Fe3+ ions replace Ni sites in the hydrous oxide lattice, forming single-phase materials.