The synthesis of the first example ()la block copolymer based on a polymer using fullerene as a backbone repeat subunit is demonstrated A facile route incorporating the electron acceptor and high fullerene content polymer, poly{(1,4-fullerene)-alt-[1,4-dimethylene-2,5-bis(cyclohexylmethylether)phenylene]} (PFDP), with the archetypal electron donor, poly(3-hexylthiophene) (P3HT), into a multiblock copolymer (M BC) structure is presented alpha,omega-Bromomethyl-PFDP was prepared by atom-transfer radical addition polymerization (ATRAP) and then reacted with alpha,omega-phenol-P3HT via a Williamson condensation to yield the MBCs The lengths of the electron-acceptor and donor polymer blocks could be selected so that the resulting solid state domains were of a size appropriate to organic solar cells Also 11 was found that the MBCs gave a wide range of macro-structures, from micelles to well-defined wires, depending on the preparation conditions.