At this aim the current–time transients referred to the growth best conditions have been fitted using a mathematical equation that considers two contributions corresponding to 3D progressive nucleation under diffusion control and to 3D instantaneous nucleation controlled by charge transfers. The atomic force microscopy study performed on the polymeric films at various stages of electrodeposition supported the proposed growth model. The structural feature and the electrochemical performance of the PEDOT:PSS systems have been studied by Raman spectroscopy and cyclic voltammetry. These studies showed that the adopted experimental conditions allow one to grow PEDOT:PSS films in their oxidized state and characterized by high-capacitive properties.