All inorganic CsPbBr3 superstructures (SSs) have attracted much research interest due to their unique photophysical properties, such as their large emission red-shifts and super-radiant burst emissions. These properties are of particular interest in displays, lasers and photodetectors. Currently, the best-performing perovskite optoelectronic devices incorporate organic cations (methylammonium (MA), formamidinium (FA)), however, hybrid organic–inorganic perovskite SSs have not yet been investigated. This work is the first to report on the synthesis and photophysical characterization of APbBr3 (A = MA, FA, Cs) perovskite SSs using a facile ligand-assisted reprecipitation method. At higher concentrations, the hybrid organic–inorganic MA/FAPbBr3 nanocrystals self-assemble into SSs and produce red-shifted ultrapure green emissions, meeting the requirement of Rec. 2020 displays. We hope that this work will be seminal in advancing the exploration of perovskite SSs using mixed cation groups to further improve their optoelectronic applications.