The successful synthesis is described for a donor-acceptor rod-coil block copolymer comprising blocks of poly[2,7-(9,9-dihexylfluorene)-alt-bithiophene] (F6T2) and polystyrene functionalized with fullerene (PS(C-60)) (F6T2-b-PS(C-60)). This new material was obtained by combining Suzuki polycondensation with radical addition fragmentation chain transfer. The block copolymer was characterized by nuclear magnetic resonance, gel permeation chromatography, and optical spectroscopy methods. Photophysical data for (F6T2-b-PS(C-60)) and a related block copolymer (F6T2-b-PS(PCBM)) (PCBM, phenyl-C61-butyric acid methyl ester) are reported and their performance as compatibilizers in bulk heterojunction organic solar cells is assessed. It is demonstrated that the addition of the rod-coil block copolymers to the active layer extends the operational stability of organic photovoltaic devices. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 888-903