Discovery of an efficient, practical, and flexible synthetic method to produce various important electron acceptors for low-cost organic photovoltaics (OPVs) is highly desirable. Although the most commonly used acceptor materials, such as PC61BM, PC71BM, IC60BA, bisPC61BM have been proved to be promising for the OPVs, they are still very expensive mainly due to their low production yields and limited synthetic methods. Herein, we report an unprecedented and innovative synthetic method of a variety of fullerene mono- and biscycloadducts by using manganese powder as a promotor. The reaction of fullerenes with various dibromides proceeds efficiently and selectively under very mild conditions to give the corresponding cycloadducts in good to excellent yields. The combination of manganese power with DMSO additive is crucial for the successful implementation of the present cycloaddition. Notably, the standard OPV acceptors, such as PCBMs, have been obtained in extraordinarily high yields, which cannot be achieved under the previously reported methods.