In this study we examined the rhenium electrodeposition process onto p-Si(100) from acidic media. The study was carried out by means of cyclic voltammetry and the potential-steps method from which the corresponding nucleation and growth mechanism were determined. Both methods were performed under illumination using a solar simulator for electron photogeneration. A 3D progressive nucleation, diffusion-controlled growth of rhenium films was found. Likewise, a morphologic analysis was completed for the deposits obtained at different potential values by means of atomic force microscopy. An energetic characterization through capacitance measurements (Mott-Schottky plots and parallel capacitance) of the p-Si/NO3- and p-Si/Re/NO3- interfaces was done. The photoelectrochemical reduction of nitrate ions, PERN, on the different p-Si/Re electrode systems synthesized was studied. An overpotential decrease of 0.3 V and a photocurrent increase for the PERN on p-Si(100)/Re electrode systems compared with p-Si(100) and metallic Re was found. Finally, the kinetic parameters of the cathodic reactions in the p-Si and p-Si/Re acidic media were estimated using intensity modulated photocurrent spectroscopy. A brief analysis from this technique was done. According to these results, the p-Si/Re electrode system could be a potential photoelectrocatalyst for the PERN.