A series of indole-substituted fulleropyrrolidine derivatives with different side groups on a pyrrolidine rings, including methyl (OIMC60P), benzyl (OIBC60P), 2,5-difluoroinebenzyl (OIB2FC60P), and 2,3,4,5,6-pentafluoroinebenzyl (OIB5FC60P), have been synthesized and used as electron acceptor in the active layer of polymer-fullerene solar cells to investigate the effect of various substitute groups on the electronic structures, morphologies, and device performances. Optical absorption, electrochemical properties and solubility of the fullerene derivatives have been explored and compared. The inverted photovoltaic devices with the configuration ITO/ZnO/Poly(3-hexylthiophene)(P3HT):[60] fullerene derivatives/MoO3/Ag have been prepared including the reference cell based on the P3HT:methyl [6,6]-phenyl-C61-butylate (PCBM) blend films. All the devices properties were measured in air without encapsulation. We also investigated the effect of the thermal annealing on the crystallinity and morphology of the active layer and the device performance. The device based on the blend film of P3HT and OIBC60P showed a power conversion efficiency of 2.46% under illumination by AM1.5G (100 mW/cm(2)) after the annealing treatment at 120 degrees C for 10 min in air. (C) 2012 Elsevier B. V. All rights reserved.