Inorganic perovskite solar cells (PSCs) have witnessed great progress in recent years due to their superior thermal stability. As a representative, CsPbI2Br is attracting considerable attention as it can balance the high efficiency of CsPbI3 and the stability of CsPbBr3. However, most research employs doped charge transport materials or applies bilayer transport layers to obtain decent performance, which vastly complicates the fabrication process and scarcely satisfies the commercial production requirement. In this work, all-layer-doping-free inorganic CsPbI2Br PSCs using organic ligands armored ZnO as the electron transport materials achieve an encouraging performance of 16.84%, which is one of the highest efficiencies among published works. Meanwhile, both the ZnO-based CsPbI2Br film and device show superior photostability under continuous white light-emitting diode illumination and improved thermal stability under 85 °C. The remarkable enhanced performance arises from the favorable organic ligands (acetate ions) residue in the ZnO film, which not only can conduce to maintain high crystallinity of perovskite, but also passivate traps at the interface through cesium/acetate interactions, thus suppressing the photo- and thermal- induced perovskite degradation.