Electropolymerization of aniline on poly(o-aminophenol)(POAP)-coated gold and indium-doped tin oxide (ITO)-coated glass electrodes yields polyaniline(PANI)/POAP two-layer composite films, exhibiting reversible redox functions in aqueous acidic solution. The PANI deposition on the POAP-coated electrodes was monitored by cyclic voltammetry (CV) and in situ UV–vis spectroelectrochemistry. CV results show that PANI/POAP composite films exhibit better stability as compared to PANI films during potential cycling in aqueous acidic solutions. Characteristic UV–vis and Raman features of the composite films have been identified and their dependencies on the electrode potential are discussed. They were significantly different from the corresponding spectral characteristics of PANI and POAP films alone.