The structure of cobalt formed by electrodeposition and the influence of the pH of the plating solution and the cathode potential was studied by potentiodynamic measurements and X-ray diffraction. It was found that the level of overpotential significantly affects the structure of the formed cobalt. When electrodeposition is performed far from equilibrium conditions, i.e., at a high overpotential, face-centered cubic (fcc) cobalt is deposited while at low overpotential hexagonal close packed Co is formed with a lower rate of hydrogen evolution. A higher overpotential is needed in a neutral compared to acidic solution in order to enhance the evolution of hydrogen that is required for the formation of fcc cobalt. (C) 2002 The Electrochemical Society.