Electron transport layer plays a key role in improving charge extraction efficiency and inhibiting electron-hole recombination in perovskite solar cells. In this study, Ce ion was doped into compact TiO2 layer to improve electron transport performance of TiO2 thin film. Through UV-Vis and UPS tests, it was found that TiO2 obtained an appropriate band position after Ce ions doping. Specially speaking, Ce-doped TiO2 band position facilitates electron transport at the interface. As a result, the device based on 0.009 M Ce-TiO2 shows the power conversion efficiency is 16.18%, which is 5.75% higher than the device without Ce ions doping. In this work, we provided a new method to improve the electron extraction rate of TiO2 thin film, which is beneficial for performance of the devices.