Inorganic perovskite solar cells show excellent thermal stability, but the reported power conversion efficiencies are still lower than for organic–inorganic perovskites. This is mainly caused by lower open‐circuit voltages ( V OC s). Herein, the reasons for the low V OC in inorganic CsPbI 2 Br perovskite solar cells are investigated. Intensity‐dependent photoluminescence measurements for different layer stacks reveal that n–i–p and p–i–n CsPbI 2 Br solar cells exhibit a strong mismatch between quasi‐Fermi level splitting (QFLS) and V OC . Specifically, the CsPbI 2 Br p–i–n perovskite solar cell has a QFLS– e · V OC mismatch of 179 meV, compared with 11 meV for a reference cell with an organic–inorganic perovskite of similar bandgap. On the other hand, this study shows that the CsPbI 2 Br films with a bandgap of 1.9 eV have a very low defect density, resulting in an efficiency potential of 20.3% with a MeO–2PACz hole‐transporting layer and 20.8% on compact TiO 2 . Using ultraviolet photoelectron spectroscopy measurements, energy level misalignment is identified as a possible reason for the QFLS– e · V OC mismatch and strategies for overcoming this V OC limitation are discussed. This work highlights the need to control the interfacial energetics in inorganic perovskite solar cells, but also gives promise for high efficiencies once this issue is resolved.