Abstract CsPbI 2 Br perovskite is known for its advantages over its organic‐inorganic hybrid counterpart including better thermal stability and appropriate bandgap for the front sub‐cell of tandem solar cell. However, its lower‐than‐satisfactory efficiency, problematic phase stability and sensitivity to moisture hinder its further advancement. Here, three kinds of glycine halides (Gly‐ X : X = Cl, Br, and I) are strategically deigned to improve the performance of CsPbI 2 Br perovskite solar cells (PSCs). Systematic experimental and calculated results prove that a 2D/3D hybrid structure is formed, wherein the Gly‐X‐based 2D perovskite is mainly located at the CsPbI 2 Br grain boundaries, and the A‐sites of the 2D perovskite form strong bonds with the 3D perovskite to suppress ion migration by increasing its activation energy. As a result, a power conversion efficiency (PCE) of 17.26% was obtained with an open‐circuit voltage ( V OC ) of 1.33 V, which is among the best PCE values for the CsPbI 2 Br PSCs. In addition, the efficiency of encapsulated device decrease only by 14.1% after 340 h continuous illumination in ambient conditions, representing one of the most‐stable inorganic PSCs reported so far. This work provides important insights into designing passivating agents to address the issue of phase segregation for the development of highly stable perovskite optoelectronic devices.