As the electron transport layer (ETL) of perovskite solar cells, oxide semiconductor zinc oxide (ZnO) has been attracting great attention due to its relatively high mobility, optical transparency, low-temperature fabrication, and good environment stability. However, the nature of ZnO will react with the patron on methylamine, which would deteriorate the performance of cells. Although many methods, including high-temperature annealing, doping, and surface modification, have been studied to improve the efficiency and stability of perovskite solar cells with ZnO ETL, devices remain relatively low in efficiency and stability. Herein, we adopted a novel multistep annealing method to deposit a porous PbI2 film and improved the quality and uniformity of perovskite films. The cells with ZnO ETL were fabricated at the temperature of <150 °C by solution processing. The power conversion efficiency (PCE) of the device fabricated by the novel annealing method increased from 15.5 to 17.5%. To enhance the thermal stability of CH3NH3PbI3 (MAPbI3) on the ZnO surface, a thin layer of small molecule [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was inserted between the ZnO layer and perovskite film. Interestingly, the PCE of PCBM-passivated cells could reach nearly 19.1%. To our best knowledge, this is the highest PCE value of ZnO-based perovskite solar cells until now. More importantly, PCBM modification could effectively suppress the decomposition of MAPbI3 and improve the thermal stability of cells. Therefore, the ZnO is a promising candidate of electron transport material for perovskite solar cells in future applications.