One new hybrid supramolecular-based phase transition compound TAPC containing macrocycle stator with electrical bistability between high and low dielectric states (TAPC = [(TAP-NH₃)·(18-crown-6)·0.5(H₂O)]·2(ClO₄) (1), TAP-NH₃ = 4-ammonio-2,2,6,6-tetramethylpiperidinium) has been prepared and characterized by variable-temperature crystal structure determination, elemental analysis, differential scanning calorimetry (DSC) and temperature-dependent dielectric spectroscopy. The DSC measurement showed a pair of sharp peaks at 357 K (heating) and 322 K (cooling), indicating that TAPC undergoes a reversible first-order phase transition. The crystal structures obtained at 293 K and 368 K are both monoclinic in the P2₁/m space group. The most distinct difference between room-temperature and high-temperature structures is the order–disorder transition of the ClO₄⁻ anions and the displacement of the guest water molecules, which are the driving forces of the high-temperature phase transition with electrical bistability (two incentives that synergistically induced the phase transition). This functional moiety could be a cation/anion or guest molecule solely, observed in a lot of compounds, and very few of them belong to the collaborative type (order–disorder motion and displacement) with high-temperature dielectric phase transitions. In addition, the large thermal hysteresis of 37.2 K contributes to a widely tunable transition between high and low dielectric states. Such distinctive dielectric performance suggests that 1 might be a potential high-temperature switchable dielectric material.