The importance of interfacial engineering as a new strategy for improving the power conversion efficiencies (PCEs) of planar-heterojunction (PHJ) perovskite solar cells is highlighted in this study. With our optimized interfacial modification, we demonstrated efficient PHJ perovskite solar cells with a high PCE of 12.2% using a sol–gel-processed ZnO ECL modified by [6,6]-phenyl C61 butyric acid methyl ester (PCBM).