An electron transport layer is essential for effective operation of planar perovskite solar cells. In this Article, PW12-TiO2 composite was used as the electron transport layer for the planar perovskite solar cell in the device structure of fluorine-doped tin oxide (FTO)-glass/PW12-TiO2/perovskite/spiro-OMeTAD/Au. A proper downward shift of the conduction band minimum (CBM) enhanced electron extraction from the perovskite layer to the PW12-TiO2 composite layer. Consequently, the common hysteresis effect in TiO2-based planar perovskite solar cells was significantly reduced and the open circuit voltage was greatly increased to about 1.1 V. Perovskite solar cells using the PW12-TiO2 compact layer showed an efficiency of 15.45%. This work can contribute to the studies on the electron transport layer and interface engineering for the further development of perovskite solar cells.