A series of multifunctional photoluminescent materials, pyrrolidinium2MnBr4 (1), N‐methylpyrrolidinium2MnBr4 (2), and N‐methylpyrrolidiniumMnBr3 (3), were obtained by means of regulating diverse organic cations and different coordination modes of inorganic metal ions. Interestingly, compounds 1, 2, and 3 exhibit different dielectric switching and relaxation behavior in the process of structural transformations. Furthermore, compounds 1, 2, and 3 possess intriguing photoluminescence properties. When subjected to UV light, tetrahedrally coordinated compound 1 shows extraordinarily strong green light emission with a high quantum yield of 51.41 %. By changing the organic cation, compound 2 exhibits an unusual orange emission under ultraviolet excitation, which is different from that of conventional tetrahedrally coordinated manganese‐based compounds. By the regulation of coordination modes of inorganic metal ions, octahedrally coordinated compound 3 emits bright red light with a high quantum yield of 36.76 %. This finding may open a new approach toward designing multifunctional photoluminescent materials. Three compounds not only exhibit different dielectric behavior but also reveal interesting photoluminescence properties. Compound 1 shows strong green light emission, compound 2 exhibits unusual orange emission, and compound 3 has bright red emission.