The synthesis of a new ionic plastic crystal, tetraethylammonium-d(20) d-10-camphorsulfonate, is reported. The crystal has three solid phases, the structures of which were determined by single-crystal X-ray diffraction (XRD). XRD analysis revealed a phase transition from nonpolar space group P2(1)2(1)2 to polar space group P2(1) with increasing temperature. The dynamics of the d-10-camphorsulfonate anion and the tetraethylammonium-d(20) cation was investigated by variable-temperature H-1 and H-2 solid-state NMR spectroscopy. The anion showed swing motion in high-temperature phases, which is in good agreement with the disorder observed in XRD analysis. The cation showed uniaxial rotation even in the low-temperature phase. The rotation axis of the tetrahedral structure showed a transition from the two-fold axis to the three-fold axis with the phase transition.