We have prepared a novel bithiophene carrying a fulleropyrrolidine substituent. Its electrochemical polymerization affords an electron donor-acceptor material that has been studied by means of electrochemical and spectroscopic techniques. The results from photoinduced absorption (PIA) and light-induced electron spin resonance (LESR) experiments demonstrate a photoinduced electron transfer from the polythiophene backbone to the tethered acceptor moieties.