AbstractOrganic‐inorganic hybrid multifunctional materials have received significant attention due to their potential applications in smart devices such as phase‐change memory (PCM), resistive random‐access memory (ReRAM). Yet, devices application requires achieving a balance between fast switching speeds, long‐term stability, and high cycling endurance in materials still facing difficulties. Herein, we report two hybrid phase transition compounds: (CMQ)BiCl₅(CMQ=Chloromethyl Quinuclidin‐3‐one) (1) and (FMQ)₂SbBr₅(FMQ=Fluoromethyl Quinuclidin‐3‐one) (2), both two compounds exhibit high phase transition temperature, dual‐stable behavior in dielectric during reversible phase transition process. Notably, 1 exhibit small dielectric change after multiple dielectric state switching. Furthermore, investigate the influence of halogen substitution (F to Cl) for compound properties, which show an Increasing transition temperature (9 K) and raising structural dimension (0D to 1D). Additionally, using first principles, analyze the electronic structure of 1 and find that it has a 3.4 eV wide bandgap, closing to GaN semiconductor (3.4 eV). This work provides a new insight into developing the next‐generation phase transition compounds and chemical modification enhances material performance.