Defect passivation is one of the most important strategies to boost both the efficiency and stability of perovskite solar cells (PSCs). Here, nontoxic and sustainable forest-based biomaterial, betulin, is first introduced into perovskites. The experiments and calculations reveal that betulin can effectively passivate the uncoordinated lead ions in perovskites via sharing the lone pair electrons of hydroxyl group, promoting charge transport. As a result, the power conversion efficiencies of the p-i-n planar PSCs remarkably increase from 19.14% to 21.15%, with the improvement of other parameters. The hydrogen bonds of betulin lock methylamine and halogen ions along the grain boundaries and on the film surface and thus suppress ion migration, further stabilizing perovskite crystal structures. These positive effects enable the PSCs to maintain 90% of the initial efficiency after 30 days in ambient air with 60%+/- 5% relative humidity, 75% after 300 h aging at 85 degrees C, and 55% after 250 h light soaking, respectively. This work opens a new pathway for using nontoxic and low-cost biomaterials from forest to make highly efficient and stable PSCs. (C) 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.