“…Organic–inorganic hybrid perovskite solar cells (PSCs) have attracted extensive attention due to their unique semiconductor properties, such as long charge carrier diffusion length, tunable bandgap, high defect tolerance, and low exciton binding energies. − Within a very short time span, impressive achievements in photovoltaic applications have been made, and the certificated power conversion efficiency (PCE) of single-junction PSCs has been rapidly increased to 26.1%, which is comparable to that of Si-based solar cells. − However, the poor long-term operational stability still restricts their practical application, largely because of the usage of humidity-/heat-sensitive organic methylammonium and formamidinium. − Substituting organic cations with volatile-free Cs + to fabricate all-inorganic perovskites (CsPbX 3 , X = I, Br, Cl, or mixed) is an effective strategy to settle this issue. , Generally, there is a positive correlation between I doge and corresponding PCE owing to the reduced bandgap but a negative relationship for environmental stability. Although the efficiency of CsPbI 3 -based PSCs has exceeded 20%, the phase instability, which suffers from the phase conversion from the photoactive α-perovskite phase to the nonphotoactive β-perovskite phase, is still a great challenge for future deployment. ,, On the contrary, CsPbBr 3 exhibits the most superior stability, but its PCE is restricted by a narrower light-absorbing range .…”