Copolymers of 1-naphthylamine (NPA) with aniline (ANI) and o-toluidine (OT) were deposited on platinum electrode in 1 M perchloric acid (HClO4) through cyclic voltammetry. The cyclic voltammograms of the copolymer showed a dominant redox couple at a midpoint potential of ca. 0.38 V with a peak separation ranging from 40 to 100 mV. Copolymerization was found to be possible only at low NPA to ANI or OT ratio. UV-visible spectroelectrochemical study on the copolymer films prepared using different feed ratios of NPA revealed the presence of NPA units in varying proportion in the copolymer. The copolymers possess both electrochemical and spectroelectrochemical properties of PNPA and PANI/POT.