Layered lead-halide organic-inorganic hybrid perovskites have shown great application prospects in photo-voltaics and optoelectronics because of their diverse structural assemblies and richness in physical properties. In this report, a rare corrugated layer lead bromide hybrid perovskite of (demethyltropinone) 4Pb3Br10 was discovered undergoing a high-temperature reversible phase transition at 410 K, which is induced by the order-disorder transition of organic cation response to the variation of external temperature. The title compound exhibits prominent switchable dielectric behavior, coupled with semiconducting property and brilliant orange fluorescence under UV excitation. The integrated multifunction ability indicates the emergence of new promising materials and provides new fertile ground to discover more potentially useful materials.