A novel methodology, through which fullerenes are effectively introduced directly onto semiconducting species, is presented herein. Electron accepting perfluorophenyl-quinolines either as small molecules, as homopolymers, or as random copolymers with regioregular poly(3-alkyl thiophene), have been synthesized and further employed for the preparation of hybrid materials with C₆₀ or PCBM. More specifically, via this route one of the fluorine atoms of the perfluorophenyl ring is transformed into an azide that undergoes [3+2]-cycloaddition onto the fullerene's surface, producing 1,6-azo bridged carbon nanostructure–organic semiconducting hybrids.