AbstractThe hybrid switchable materials induced by dielectric phase transition are always an important scientific topic for their potential applications in the flexible sensor and devices. And the organic cations and anions can interact effectively, which is conducive to the functional development in the organic‐inorganic hybrid crystal state. In which, the flexible organic cations are more likely to undergo dynamic motion such as order‐disorder transformation and reorientation under temperature stimulation. Here, we chose 1‐methylpiperidinium as flexible organic cation, and then successfully designed a new organic‐inorganic hybrid crystal [1‐methylpiperidinium]2[ZnCl4] (compound 1), which displays a phase‐transition packing structure. It′s worth pointing out that compound 1 undergoes a reversible phase transition at 393.8 K accompanied with a conspicuous dielectric response. The dielectric constant can switch rapidly and reversibly between high and low dielectric states with excellent cycle stability. We believe that the report of compound 1 is conducive to the design of new series of switching materials.