Novel fullerene-grafted poly(3-hexylthiophene) (P3HT)-based rod-coil block copolymers have been synthesized. The regioregular P3HT rod block has been synthesized by a modified Grignard metathesis reaction (GRIM). An original in situ end-capping reaction has been developed in order to convert the P3HT block into an efficient macro-initiator for the nitroxide-mediated radical polymerization (NMRP) of the coil block. Controlled radical polymerization of the second poly(butylacrylate-stat-chloromethylstyrene) [P(BA-stat-CMS)] block has been done through various conditions leading to different coil block lengths. The final electron donor-acceptor block copolymer has been obtained after C-60 grafting in soft conditions. Copolymers have been characterized by H-1 NMR and size exclusion chromatography. Optical characterizations, before and after C-60 grafting, are reported.