A series of arylated dihydrofullerene derivatives were synthesized to elucidate the effective design of fullerene derivatives for enhancing the performance of organic photovoltaics. The LUMO energy of the fullerenes was estimated by the first reduction potential and theoretical calculations. The results showed that the methoxy groups substituted at spatial proximity to the fullerene core offered significant stabilization of the LUMO level. The stabilizing effect of the directly arylated fullerenes is more significant than that of conventional methanofullerenes. The theoretical investigation was performed with regard to the electronic interaction between the methoxy and fullerene moieties.