A donor-acceptor, rod-coil diblock copolymer has been synthesized with the objective of enhancing the photovoltaic efficiency of the PPV-C-60 (PPV = poly(p-phenylenevinylene)) system by the incorporation of both components in a molecular architecture that is self-structuring through microphase separation. Diblock copolymers were obtained by using an end-functionalized rigid-rod block of poly(2,5-dioctyloxy-1,4-phenylenevinylene) as a macroinitiator for the nitroxide-mediated controlled radical polymerization of a flexible poly(styrene-stat-chloromethylstyrene) block. The latter block was subsequently functionalized with C-60 through atom-transfer radical addition. In a spin-cast film of the final diblock copolymer, the luminescence from PPV is strongly quenched, indicating efficient electron transfer to C-60 under suitable conditions, solution-cast films of these diblock copolymers exhibit micrometer-scale, honeycomb-like patterns of holes.