Bistable optical-electrical duplex switches represent a class of highly desirable intelligent materials because of their potential applications in the fields of next-generation flexible devices. However, controllable photoelectric switchable materials with high-performance dielectric-switching and optical-switching properties are still scarce, with triplex bistable switches being rarely reported. Herein, a novel optoelectronic triple-functional organic-inorganic material, 5-azonia-spiro[4,4]nonane tetrabromomanganese (1, [ASN]2[MnBr4], ASN = (CH2)4N(CH2)4), which undergoes a reversible solid-state phase transition around 327 K and exhibits a recognizable second harmonic generation (SHG) effect between SHG-on and SHG-off states, has been successfully synthesized and grown as block crystals. Intriguingly, the bromine-doped crystal can exhibit intense green luminescence with a high quantum yield of 13.07% under UV excitation, extending its application in the field of photoelectric seamless integration and/or flexible multifunctional devices.