Solid-to solid-state reversible phase transitions are widely used in switchable dielectrics, ferroelectrics, piezoelectrics, and pyroelectric and non-linear optical materials. Herein we report a new crown ether clathrate, [Habf-(18-crown-6)1.5]+ [PF6]- (Habf = p-ammonium benzene formamide) which shows an interesting reversible phase transition near room temperature (263 K). X-ray single crystal diffraction analysis shows that the synergetic rotation motion between the 18-crown-6 crown ethers and the order-disorder motions of both hexafluorophosphate guest anions and 18-crown-6 crown ether host molecules lead to the phase transition. This reversible phase transition is confirmed by an evident thermal anomaly behavior around 263 K. The apparent step-like dielectric change around the phase transition indicates that it has potential application in dielectric switches.