Ethylenediamine (EDA) functionalized fullerene nanoparticles as independent electron transport layers (ETLs) for inverted polymer solar cells exhibited high electronic conductivity and low work function. Compared with ZnO, the power conversion efficiency of the devices based on PTB7-Th:PC₇₁BM was increased from 9.1% to 10.06% with C₆₀–EDA ETLs and to 9.49% with Gd@C₈₂–EDA, mainly due to the greatly improved short current density.