The structure and transport of N-propyl-N-methylpyrrolidinium tetrafluoroborate (P<sub>13</sub>BF<sub>4</sub>) has been investigated over a wide temperature range in consequence to exhibiting properties suitable for potential solid-state superionic electrolyte applications. Prior to melting, the organic salt, P<sub>13</sub>BF<sub>4</sub>, transforms into a plastic crystal phase. Intrinsic conductivity in this solid, phase I (45–65 °C), is comparable to that in the melt (<sub>~</sub>10<sup>−3</sup> S cm<sup>−1</sup>). Ionic motion and transport properties were investigated by <sup>1</sup>H and <sup>11</sup>B nuclear magnetic resonance (NMR) spectroscopy. Pressure-induced plastic flow in this system may accommodate volume changes in device application and to this extent, X-ray diffraction (XRD) has been used. Scanning electron microscopy (SEM) revealed complex surface morphology and lattice imperfections associated with the strong orientational disorder of the plastic state.<br>