Two new zinc‐based hybrid organic‐inorganic compounds (AZT)2[ZnX4] (AZT = azetidine cation; X = Cl, 1; Br, 2) were successfully synthesized as high‐temperature stimuli‐responsive materials. Systematic thermodynamic characterization demonstrated that they undergo reversible structural phase transitions accompanied by switchable dielectric constant centered at 342 K for 1 and 356 K for 2, respectively. Variable‐temperature single‐crystal X‐ray analysis and dielectric constant measurements disclosed the order‐disorder transformation of the cation and anion contributed to the desirable electrical properties. As expected, the static‐motional transition in crystal structure arouses dielectric transitions between the low‐ and high‐dielectric states, making them a type of switchable dielectric materials.