To study the phase behavior and role of defects in the ion conduction of a well-investigated plastic crystal electrolyte, we measured the low-temperature heat capacities of quinuclidinium hexafluorophosphate ([HQ]PF6) plastic crystal and the defects of pure [HQ]PF6 and its mixtures containing lithium ions and chloride ions. The heat capacities of the pure material show two solid‒solid phase transitions at room temperature and a low temperature. Positron annihilation lifetime spectroscopy (PALS) revealed the phase dependence of the defect size for both the pure material and the mixtures. The defects in these two mixtures expand largely to approximately 2 (with Li+) and 2.5 (with Cl−) times larger than those in the pure material. The relationships between the ionic conductivity and vacancy volume of the pure material and the mixtures obey the Cohen−Turnbull free volume model, which is also phase dependent. This work help elucidate defect-assisted ion transfer in organic ionic plastic crystals.