Abstract We synthesized a new 56-π-electron fullerene derivative through a Diels–Alder cycloaddition of benzo [c] thiophene that featured a relatively low temperature, closer to stoichiometric use of the diene, and easy product purification. The 56-π-electron benzo [c] thiophene diadduct (BTCDA) has a LUMO energy level of 0.09 to 0.18 eV higher than that of 58-π-electron fullerenes, and therefore, the BTCDA-based organic photovoltaic device ...