This article focuses on the synthesis, design concepts and photovoltaic performance of fullerene-based electron acceptors used in solution processed bulk heterojunction organic solar cells. Excellent fullerene acceptors such as 56π-electron conjugated dihydromethanofullerene derivatives, ICBA, methano-indene-fullerenes, mix-PCBM are introduced from a synthetic chemistry viewpoint in addition to fullerene chemistry background being offered, which should benefit a wide range of organic solar cell research.