A design of experiments was employed to optimize the conditions of synthesis in order to electrogenerate thick polypyrrole films suitable for application as a cathode in polymeric batteries or supercapacitors. The influence of five main variables: potential of polymerization, generation time, monomer concentration, electrolyte concentration, and temperature, and their second-order interaction on the specific charge were studied and optimized through three stages. The initial stage requires the synthesis of 16 films (design matrix). Every film is weighed and checked in the background solution to obtain the stored charge and the specific charge. The resulting statistical significance shows that optimization only is possible at low potentials. In a second stage a design matrix with eight new experiments allowed the determination of the variables of synthesis affecting the specific charge and the direction of change of those variables to optimize this property. By changing the conditions of synthesis in that direction three more experiments resulted in a designed film 0.5 mu m thick and 104 Ah kg-l