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The high power-conversion efficiencies of hybrid perovskite solar cells encourage many researchers. However, their limited photostability represents a serious obstacle to the commercialization of this promising technology. Herein, we present an efficient method for improving the intrinsic photostability of a series of commonly used perovskite material formulations such as MAPbI3, FAPbI3, Cs0.12FA0.88PbI3, and Cs0.10MA0.15FA0.75PbI3 through modification with octenidine dihydroiodide (OctI2), which is a widely used antibacterial drug with two substituted pyridyl groups and two cationic centers in its molecular framework. The most impressive stabilizing effects were observed in the case of FAPbI3 and Cs0.12FA0.88PbI3 absorbers that were manifested in significant suppression or even blocking of the undesirable perovskite films' recrystallization and other decomposition pathways upon continuous 110 mW/cm2 light exposure. The achieved material photostability—within 9000 h for the Oct(FA)n−1PbnI3n+1 (n = 40–400) and 20,000 h for Oct(Cs0.12FA0.88)n−1PbnI3n+1 (where n = 40–400) formulations—matches the highest values ever reported for complex lead halides. It is important to note that the stabilizing effect is maintained when OctI2 is used only as a perovskite surface-modifying agent. Using a two-cation perovskite composition as an example, we showed that the performances of the solar cells based on the developed Oct(Cs0.12FA0.88)399Pb400I1201 absorber material are comparable to that of the reference devices based on the unmodified perovskite composition. These findings indicate a great potential of the proposed approach in the design of new highly photostable and efficient light absorbers. We believe that the results of this study will also help to establish important guidelines for the rational material design to improve the operational stability of perovskite solar cells. [ABSTRACT FROM AUTHOR]