In this work we report electrochemical copolymerization of thiophene (Th) with thiophene-substituted fulleropyrrolidine (C-60-ThFP) on Pt electrode from dichloromethane solution. A structure of the resultant donor-acceptor copolymer with high fullerene content, corresponding to one C-60-ThFP per two thiophene units was determined by XPS and FTIR spectroscopy. The ratio of the two monomers in the polymer film was independently determined by electrochemical quartz crystal microbalance. Electroactivity of C-60-ThFP and copolymer film in p-and n-doping ranges was studied by cyclic voltammetry. Geometry of a representative fragment of the synthesized copolymer was simulated by means of DFT calculations. (C) 2014 Elsevier Ltd. All rights reserved.