Interfacial compatibility between the electrode and organic semiconductor plays a critical role in controlling the charge transport and hence efficiency of organic solar cell. Here, we introduce a novel small-molecule zwitterionic electrolyte (S1) combined with ZnO as electron transporting interlayer employed for the inverted PTB7:PC71BM bulk heterojunction solar cell. The resulting device with the S1/ZnO stacked interlayer achieves a high PCE of 8.59%, obtaining a 16.2% improvement over the control device performance of 7.4% without the S1 attributed to the significant increased short-circuit current density and fill factor. The interfacial properties are investigated. It is found that the S1/ZnO interlayer possess an ultralow work function of 3.6 eV, which originates from the interfacial double dipole step induced by the zwitterionic side chain electrostatic realignment at interface. The S1/ZnO interlayer exhibits the excellent charge extraction ability, suppresses the charge recombination loss and decreases the series resistance at the active layer/electrode contact.