The organic‐inorganic hybrid compounds, [Cu2Cl6]2– (1), [Fe2Cl6O]2– (2), and [FeCl4]– (3), based on [(C8H12NO)(18‐crown‐6)]+ (C8H12NO = 4‐methoxybenzylammonium) supramolecular cations, were synthesized and structurally characterized. Crystal structure analyses and thermal and dielectric studies showed that compounds 1 and 2 have similar crystal packings and undergo reversible phase transitions at 230 K and 358 K, respectively. Compound 3 shows a phase transition at 361 K, though its crystal structure is remarkably different from 1 and 2. These results indicate that the phase transitions may arise from the [(C8H12NO)(18‐crown‐6)]+ supramolecular cations. The role of the chlorometalate anions is to tune the crystal packings and thus the phase transition points and types.