By an oxidative coupling polymerization approach, we have synthesized an electroactive polymer with good solubility containing alternating phenyl-capped aniline pentamer in the main chain and azo chromophores in the side chain. In this study, we present reversible example of photochemically induced switching of electroactivity by performing electrochemical CV in two ways: (i) in that the photochemical reaction switch can be photochemically reverted by reirradiation at a different wavelength (ii) in that a photoreaction is used that is thermally reversible. At the same time, electrochemical investigations of electrochromic properties of an aniline-pentamer-based electroactive poly(azine-azo) (EPAA) coating prepared by oxidative coupling polymerization are presented. The in-situ chemical oxidation of the reduced form of soluble, electroactive poly(azine-azo) (EPAA) in N-methyl-2-pyrrolidone (NMP) was monitored by UV-Visible absorption spectra. Moreover, the electrochromic performance of EPAA was investigated by measuring electrochromic photographs and UV absorption spectra. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.