The first stages of electrodeposition of zinc-cobalt alloys on highly oriented pyre-graphite are studied by tapping mode atomic force microscopy (AFM), scanning electron microscopy, and electrochemical analysis. Low Zn(II)/Co(II) ratio (1/9) solutions are selected for this study. Potentiostatic deposition begins through the formation of randomly distributed zinc-rich nuclei on the surface, showing exclusion areas around the larger nuclei and preferential nucleation at the kink sites. At long deposition times an incipient dendritic growth, related to the intiation of pure cobalt deposition is observed. A simple AFM tip deconvolution model is used to obtain the actual dimensions of both the tip itself and the deposited nuclei. The nuclei growth mechanism observes lateral diffusion and aggregation and the formation of emerging nuclei on top of yet consolidated nuclei.