Polystyrene-functionalized C60 (C60-PS) was synthesized by atom-transfer radical polymerization. The structure of the hybrid was characterized by gel permeation chromatography and thermal gravimetric analysis. The self-assembly of polystyrene-block-poly(ethylene oxide) (PS-PEO)/C60-PS film in annealing solvents was studied on a silicon wafer and at the air/water interface by transmission electron microscopy. The method is an easy route to produce arrays of ordered nanostructures. The addition of C60-PS has a great effect on the self-assembly of PS-PEO. Treating the film under solvent vapor can modulate the orientation and ordering of PS-PEO microdomains. The C60-PS enhanced the formation of lamellae microstructure, and the C60-PS entered the PS phase, expanding the scale of PS domains. Nevertheless, it becomes more complex when it refers to the self-assembly at the air/water interface under solvent vapor for a long time. The selectivity of solvent to the polymer chains plays an important role as the annealing time increases.