[en] Understanding the properties of the precursor can provide deeper insight into the crystallization and nucleation mechanisms of perovskites, which is vital for the solution-process device performance. Herein, we conducted a detailed investigation into the photophysics properties of CsPbBr${}_3$ precursors in a broad concentration and various solvents. The precursor transformed from the solution state into the colloidal state and exhibited aggregation-induced emission character as the concentration increased. The aggregative luminescence from the precursors originates from the polybromide plumbous that is formed through the coordination of solvent molecules to the lead metal center. Two adducts with monodentate (PbBr${}_2$ ⋅ solvent) and bidentate (PbBr${}_2$ ⋅ 2solvent) ligands can be obtained, accompanied by emission with photoluminescence at 610 and 565 nm, respectively. Furthermore, the aggregative luminescence intensity and color could be regulated by changing the solvent and precursor ratio. Besides, we discussed the difference between the molecular aggregate in the organic system and the ionic aggregate in the inorganic system: the ionic aggregate is composed of solvated ions rather than individual molecules as in organic systems, which could possess properties that ions do not have. The fluorescence that is sensitive to Pb${}^{2+}$ coordination reported here could be applied to screen perovskite additives and judge the precursor aging. (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH)