C60 o-quinodimethane bisadducts [C60(QM)2] are promising electron acceptors for bulk heterojuction (BHJ) organic solar cells (OSCs). However, previous production of C60(QM)2 often resulted in excessive regioisomers, which were difficult to purify and might consequently obscure the structure-performance study of the organofullerene acceptors. Herein, the electrosynthesis of C60(QM)2 is reported. The reaction exhibits a strong regiocontrol with generation of fewer regioisomers. Pure regioisomers of cis-2, trans-3, and e C60(QM)2 are obtained, and the structures are solved with single-crystal X-ray diffraction. Interestingly, the cis-2 and trans-3 regioisomers exhibit better photovoltaic performance than the e regioisomer in the OSCs based on poly(3-hexylthiophene) (P3HT), which can be correlated with their structural difference.