The surface morphology of ZnO films at different annealing temperatures and the performance of polymer solar cells (PSCs) with ZnO as the electron transport layer are studied. The low temperature sol-gel processed ZnO film has smoother surface than that in higher temperature, which results in the best photovoltaic performance with a power conversion efficiency (PCE) of 3.66% for P3HT:PC₆₁BM based solar cell. With increasing annealing temperature, the photovoltaic performance first deceases and then increases. It could be ascribed to the synergy effects of interface area, the conductivity and surface energy of ZnO film and series resistance of devices.