A new 2,5-di-(2-thienyl)-1H-pyrrole (SNS) moiety containing perylenediimide (PDI) acceptor as pendant side chain has been synthesized for an electroactive monomer and then directly deposited onto ITO/glass surface via electrochemical polymerization process. The observed electronic interaction only at the excited state due to the presence of phenylene spacer between SNS-donor and PDI-acceptor moiety leads to efficient fluorescence quenching. This charge separation behavior was also proved by theoretical DFT calculations. Thin films of the polymer electropolymerized onto transparent electrode exhibited ambipolar multi-electrochromic behavior including purple, violet-red-khaki-blue colors in both anodic and cathodic regime only between -1.2 and 1.0 V. We further demonstrated that this polymer film has a high contrast ratio (Delta T = 45% at 900 nm), a faster response (0.5 s), high coloration efficiency (254 cm(2) C-1) and retained its performance by 92% even after 5000 cycles. (C) 2014 Elsevier Ltd. All rights reserved.