Two A-B-C type conjugated amphiphilic triblock fullerene derivatives C60-2HMTPB and C60-2EHTPB were obtained in multi steps synthesis with three different blocks, and the amphiphilic diblock molecular C60-4TPB was also preferred as a reference. When as modifying layer on zinc oxide (ZnO), the three fullerene derivatives can all reduce the work function of ZnO via modulation of the interfacial dipoles and lead a better electrical coupling. As introducing treatment of toluene, the obvious self-assembly of fullerene derivatives were observed, which were supported by X-ray diffraction and contact angle of water measurement. Base on PTB7-Th:PC71BM system, the inverted organic solar cells devices with structure of ITO/ZnO/fullerene derivatives/PTB7-Th:PC71BM/MoO3/Al got power conversion efficiencies of 8.62％, 8.83％and 9.00％for C60-4TPB, C60-2HMTPB and C60-2EHTPB, respectively, compared 8.13％of devices with bare ZnO. The result of conjugated amphiphilic triblock fullerene derivatives provides a straightforward approaching by simultaneously modulating the morphology and interfacial work function of ZnO, which can also lead high performance in optoelectronic devices.