Multifunctional materials have long been a popular research area, with organic-inorganic hybrids frequently utilized due to their diverse properties and versatile assembly techniques. In this context, a novel Mn-based organic-inorganic hybrid compound (BTPA)2MnBr4(1) was prepared, with strong green photoluminescence, phase transition under thermal stimulation, and two reversible dielectric-state switches. This compound exhibits strong green photoluminescence under ultraviolet excitation, boasting a quantum yield of 44.36%. Furthermore, it demonstrates a reversible ferroelastic phase transition at 358/348 K. The integration of temperature and photosensitivity in compound 1 opens up new avenues for the development and exploration of a broader spectrum of multifunctional phase transition materials.