In this report, we demonstrate enlarged grain size (up to-3 lm) in ambient-stable black c-phase CsPbI2Br thin films through the regulated addition of guanidinium iodide (GAI) as an effective volatile additive. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) measure-ments indicate the complete sublimation of GAI following annealing, with no inclusion inside the final c-CsPbI2Br perovskite lattice. GAI is found to participate by retarding the cation-anion reaction via the Cs+ and GA+ cation-exchange process. We find that inorganic perovskite solar cells (IPSCs) devices made from (CsPbI2Br)0.925 + 0.075 GAI and a phenyltrimethylammonium chloride (PTACl) passivation retain a solar-friendly band-gap of 1.91 eV and excellent device performance, with the best open-circuit voltage reaching as high as 1.34 V, with highly reproducible and stable photo conversion efficiencies of 16.88% (for 0.09 cm2) and 15.60% (large area 1 cm2) under ambient conditions. Photostability analysis further demonstrated negligible efficiency loss over 1000 h under continuous one-sun equivalent illumination, indicating GAI additive as a promising approach toward ambient stable, all-inorganic high-efficiency solar cells.