The achievment of both high T_c (Curie temperature) and blue-white light in materials has always been a huge challenge that needs to be addressed urgently, especially in the approaching digital era led by flexible/wearable devices coupled with photoelectric features. However, this type of material has not yet been realized due to the limitations of both high T_c and flexibility. It is known that hybrid materials are superior to traditional inorganic films in super-flexibility, which has been fully demonstrated by the CH₃NH₃PbI₃ films. Herein, we overcame this challenge and synthesized the first batch of high T_c dielectric phase transition bulk/film coupled with blue-white emission through an effective cation–anion regulation. At the same time, an ideal film forming ability and flexibility were also exhibited. Additionally, the switchable phase transition mechanism and significant photoluminescence characteristics of the hybrid compound [ASD]₂[ZnBr₄] (1, ASD = 5-azonia-spiro[4,5]decane) were analysed. Furthermore, it is especially noteworthy that 1 exhibited a unique and efficient broadband blue-white light emission with a photoluminescence quantum yield (PLQY) of 18.29%. In another words, this work sheds light on a new pathway towards desirable high T_c and flexible photoelectric multifunctional materials.