Poly(p-phenylene) (PPP) and poly(p-phenylene-pyrrole) (PPP-Ppy) films were electrochemically polymerized on indium-tin-oxide glass (ITO) and platinum electrodes. Their optical properties were studied by UV-vis and photoluminescence spectroscopy. The influence of the final potential applied during synthesis (Ef) on the optical properties of PPP films was also studied. The PPP film prepared at 1.5 V showed an absorption band at 540 nm which was attributed to a p-doping process, Stable films with a similar emission band at 420 nm (blue region) were obtained after polymerization of p-terphenyl, and p-terphenyl/pyrrole monomers.