Inclusion compounds that contain dynamic polar guests possess rich electrical properties such as ferroelectricity and switchable dielectric constant upon undergoing order-disorder-type phase transitions. We here report a thiourea-based inclusion compound (Him)ij(TU) 2 Cl] (Him = imidazolium, TU = thiourea) that undergoes two reversible structural phase transitions at 139 K and 145 K, which are induced by the orderdisorder transformations of the Him cation guests in the channels formed by the anionic [(TU) 2 Cl] components. Switching of the dielectric constant is thus triggered between the low-and high-dielectric states.