The stereo-electronic control over bisadditions of conjugated polymers to fullerene (C 60 ) is explored in the formation of alternating copolymers. The chemistry, resulting configuration, and properties of poly(3-hexylthiophene)-alt-C 60 copolymers prepared by either classic pyrrolidine ring formation or an atom transfer radical addition are compared. Both routes result in controlled additions of polymers to C 60 . Extensive macromolecular modeling through PM6 methods indicate that there is no conjugation between P3HT and C 60 in the systems studied. This along with 2D-NMR, AFM, and photovoltaic characterizations of the materials indicate the importance of the structure of the modified C 60 and the nature of the linking group between C 60 and P3HT segments in determining the morphology of the copolymers in the solid state.