The electron transport layer (ETL) plays a crucial role on the electron injection and extraction, resulting in balanced charge transporting and reducing the interfacial energy barrier. The interface compatibility and electrical contact via employing appropriate buffer layer at the surface of hydrophobic organic active layer and hydrophilic inorganic electrode are also essential for charge collections. Herein, an ether chain functionalized fullerene derivatives [6,6]-phenyl-C61-butyricacid-(3,5-bis (2-(2-ethoxyethoxy)-ethoxy)-phenyl)-methyl ester (C60-2EPM) was developed to modify zinc oxide (ZnO) in inverted structure organic solar cells (OSCs). The composited ZnO/C60-2EPM interface layer can help to overcome the low interface compatibility between ZnO and organic active layer. By introducing the C60-2EPM layer, the composited fullerene derivatives tune energy alignment and accelerated the electronic transfer, leading to increased photocurrent and power conversion efficiency (PCE) in the inverted OSCs. The PCE based on PTB7-Th: PC71BM was enhance from 8.11% on bare ZnO to 8.38% and 8.65% with increasing concentrations of 2.0 and 4.0 mg/mL, respectively. The fullerene derivatives C60-2EPM was also used as a third compound in P3HT:PC61BM blend to form ternary system, the devices with addition of C60-2EPM exhibited better values than the control device.