AbstractOrganic–inorganic lead halide perovskites have shown photovoltaic performances above 20% in a range of solar cell architectures while offering simple and low-cost processability. Despite the multiple ionic compositions that have been reported so far, the presence of organic constituents is an essential element in all of the high-efficiency formulations, with the methylammonium and formamidinium cations being the sole efficient options available to date. In this study, we demonstrate improved material stability after the incorporation of a large organic cation, guanidinium, into the MAPbI₃ crystal structure, which delivers average power conversion efficiencies over 19%, and stabilized performance for 1,000 h under continuous light illumination, a fundamental step within the perovskite field.