The power conversion efficiency of perovskite solar cells (PSCs) has ascended from 3.8% to 22.1% in recent years. ZnO has been well-documented as an excellent electron-transport material. However, the poor chemical compatibility between ZnO and organo-metal halide perovskite makes it highly challenging to obtain highly efficient and stable PSCs using ZnO as the electron-transport layer. It is demonstrated in this work that the surface passivation of ZnO by a thin layer of MgO and protonated ethanolamine (EA) readily makes ZnO as a very promising electron-transporting material for creating hysteresis-free, efficient, and stable PSCs. Systematic studies in this work reveal several important roles of the modification: (i) MgO inhibits the interfacial charge recombination, and thus enhances cell performance and stability; (ii) the protonated EA promotes the effective electron transport from perovskite to ZnO, further fully eliminating PSCs hysteresis; (iii) the modification makes ZnO compatible with perovskite, nicely resolving the instability of ZnO/perovskite interface. With all these findings, PSCs with the best efficiency up to 21.1% and no hysteresis are successfully fabricated. PSCs stable in air for more than 300 h are achieved when graphene is used to further encapsulate the cells.

In the field of photovoltaic industry, organolead halide perovskite solar cells (PSCs) as cleaner and cheaper photo‐voltaic devices have shown a bright prospect with power conversion efficiency (PCE) rapidly climbing from 3.8% to certified 22.1% in a few years. Interface engineering has been proven to be highly effective to solve the instability‐to‐moisture issue and enhance the performance of PSCs. Here, this work develops a simple and easy‐proceeding strategy that depositing both aminocaproic acid [H2NCH2(CH2)4COOH, abbreviated as AmCA] and caproic acid [CH3(CH2)4COOH, CA] at the mesoporous TiO2/perovskite interface leads to significant enhancement in both the efficiency and stability of PSCs. These two organic modifiers work synergistically to enhance the overall performance of PSCs by promoting electron transfer through the interaction between amino groups on AmCA and perovskite layer, and resisting moisture with alkyl chains from CA. The champion efficiency of modified cells reaches 18.2%, with an average PCE of 17.5% in reliable reproducibility, with significant improvement in stability under 50 ± 5% relative humidity in air. The developed simple interfacial modification approach should be effective to enhance both efficiency and stability of PSCs with other architectures as well. More importantly, this scenario may provide insight into the commercialization of perovskite solar cells in the not‐too‐distant future.

N-Methyl-2-pyrrolidone (NMP), forming only one PbI2·NMP complex, is demonstrated as an excellent coordinative solvent for the fabrication of high-quality perovskite thin films.