Herein, alternating donor-acceptor type benzodithiophene and benzotriazole bearing copolymers were synthesized and thieno[3,2-b] thiophene and furan units were incorporated as pi-bridges. The application of these polymers for electrochromic and photovoltaic studies were performed. Spectroelectrochemical studies illustrate that both polymers showed multichromic behavior due to tailoring of polaron bands in visible region. Photovoltaic properties of P2 were performed by conventional device structure. The best performance device based on P2: PC71BM (1: 3, w/w) exhibited the power conversion efficiency of 2.98%, with V-oc of 0.74 V, J(sc) of 6.31 mA/cm(2), and FF of 64%. The carrier mobility of the P2: PC71BM was calculated as 1.37 x 10- 3 cm(2)/V.s via space-charge-limited current method. (C) 2017 The Electrochemical Society.