Electroactive copolymers of aniline and o-aminophenol (OAP) with varying concentration ratios prepared by potential cycling in acidic aqueous solutions of the monomers on indium-doped tin oxide (ITO) coated glass and gold electrodes were studied with in situ UV–vis and Raman spectroscopy. Characteristic UV–vis and Raman features have been identified and their dependencies on the electrode potential are discussed. Spectroelectrochemical results reveal the formation of polyaniline-based copolymers at low concentration of OAP in the feed but incorporation of more OAP units into the copolymer with higher concentration of OAP in the comonomer feed. Spectroelectrochemical features are significantly different from those of both homopolymers.