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In this work a systematic study on the kinetics of Ni electrodeposition in acid sulfate media over a wide pH range was carried out. Two distinct electrodeposition behaviors were experimentally detected as a function of pH. Accordingly, it is suggested that Ni electrodeposition takes place through different intermediates: In the lower pH range, Ni(normalI)ads species predominates at the electrode surface, and its formation is deactivated with increasing pH, whereas in less acid solutions, Ni electrodeposition occurs via two species, [Ni(OH)]ads and [Ni(OH)]ads+ . The chemical nature of Ni(normalI)ads , [Ni(OH)]ads and [Ni(OH)]ads+ species is discussed on the basis of the interfacial pH behavior.