A new molecular phase transition material, [PhCH2NH(CH3)2]2C2O4⋅H2C2O4, which undergoes a reversible phase transition at 151.6 K, has been successfully synthesized. Differential scanning calorimetry (DSC), specific heat capacity, and dielectric measurements confirm its reversible phase transition with a large thermal hysteresis of 15.1 K, demonstrating that the phase transition is typical first order. Variable‐temperature single‐crystal X‐ray diffraction analyses reveal that the order–disorder transformations of carboxy oxygen atoms induce the structural phase transition. A slight reorientation of the oxalic acid unit is discovered to accompany the ordering of carboxy oxygen atoms at low temperature. The DSC measurement result of the deuterated analog is different to that of 1, indicating that proton dynamic motions in hydrogen bonds also contribute to the phase transition.