In this study, we examined the synthesis of Prussian blue onto p-Si(100). The Prussian blue formation was carried out by means of the deposition of a Fe film and then its dissolution in presence of potassium hexacyanoferrate(II). In the first stage, a study by cyclic voltammetry was carried out, and then, using the potential step method, the corresponding nucleation and growth mechanism were determined. Likewise, a morphologic analysis of the deposits obtained at different potential values by means of atomic force microscopy was carried out. The results are consistent with a 3D progressive nucleation with diffusion-controlled growth. Finally, this research is oriented to construct electrochemical storage devices which can be in situ loaded by the photovoltaic action of the semiconductor base material doped silicon.