In situ laser Raman spectra of electrochemically precipitated thin-film Ni(OH)(2) electrodes in alkaline NaOH electrolytes were recorded, and the effect of repeated charge-discharge cycling on the structure and phase composition of the discharged and charged films was investigated. Careful deconvolution analyses of the Raman and surface-enhanced Raman spectra showed that freshly precipitated films of Ni(OH)(2) contain not only an oc-like phase but also small amounts of a beta-phase. By combining cyclic voltammetry with in situ Raman spectroscopy, spectral changes that accompanied charge-discharge cycling could be associated with a partial transformation of the predominant alpha-phase into a disordered beta-Ni(OH)(2) phase. A new phase characterized by a vibration at 522 cm(-1) was also discovered in the film at the end of the cycling procedure. Analysis of the Raman spectra of the oxidized electrode (NiOOH active material) revealed for the first time a slight variation of the 477/559 cm(-1) peak pair ratio, which corresponds to phase transitions in the Ni(III) hydrous -1 oxide film, as the electrode was cycled. Significant differences between the low-frequency-region Raman spectra of chemically synthesized alpha,beta-Ni(OH)(2) and those of highly disordered hydrous Ni(OH)(2) films, as well as the absence of characteristic vibrations in the OK stretching region of the in situ Raman spectra of the Ni(OH)(2) electrode, suggest that chemically prepared alpha,beta-nickel hydroxides should not be regarded as structural models for electrochemically precipitated thin-film materials.