The electrodeposition of tin + cobalt alloys from a slightly acidic sulfate-gluconate bath on both vitreous carbon and copper substrates has been studied for different [Sn(II)]/[Co(II)] ratios in the bath, varying between 1/10 and 1/2. A relationship between the electrochemical stripping analysis and the morphology of the deposits has been found. Two different types of deposit were obtained. At low [Sn(II)]/[Co(II)] ratios and relatively high deposition rates a nodular, cobalt-rich, nanocrystalline coating was obtained, while at high [Sn(II)]/[Co(II)] ratios and low deposition rates a new, well-defined tetragonal SnCo phase was obtained, with cell parameters of a = 3.087 Angstrom and c = 5.849 Angstrom. This structure favours hydrogen evolution.