Potentiodynamic electrochemical synthesis was used to controllably synthesize nanofibers (mean diameter 48 nm) and/or nanoparticles (mean diameter 88 nm) of polyaniline (PANI) on gold electrodes. The films were characterized by cyclic voltammetry (CV), field emission gun scanning electron microscopy (FEG-SEM) and atomic force microscopy (AFM). The type and dimensions of the nanostructures depend on deposition conditions such as monomer concentration and scan rate. This study shows that the nucleation and growth steps play a key role on the film development and its nano-morphology.