LAUSR

Witnessed by the rapid increase of power conversion efficiency to 25.5%, organic–inorganic hybrid perovskite solar cells (PSCs) are becoming promising candidates of next‐generation photovoltaics. However, PSCs can be unstable under the influence of light and bias. Especially, grain boundaries (GBs) are vulnerable to attack by light and bias in perovskite films, leading to degradation of photovoltaic properties of PSCs. Herein, photocurrent atomic force microscopy and Kelvin probe force microscopy are employed to systematically investigate the bias‐dependent charge transport behaviors and stability of (FAPbI3)0.85(MAPbBr3)0.15 perovskite under working condition. Bias‐dependent morphology and photocurrent images show irreversible decomposition of the perovskite at a bias of 0.1 V or below, which is accelerated by light illumination, leading to formation of an interfacial layer that restricts carrier transport. Meanwhile, GBs appear to enhance carrier transport at larger bias, but serve as breakthrough sites for perovskite decomposition at smaller bias. Introducing excess methylammonium iodide promotes decomposition, while potassium iodide passivation greatly relieves the decomposition. These results support the ion migration mechanism of decomposition through interfaces and GBs. This work provides a deeper understanding of bias‐induced degradation of PSCs as well as bias‐dependent double‐edged roles of GBs, and forms valuable guidance for appropriate operation of PSCs.