The treatment of an organic ionic plastic crystal electrolyte <i>N</i>-methyl-<i>N</i>-ethylpyrrolidinium tetrafluoroborate (P<sub>1,2</sub>BF<sub>4</sub>) with supercritical CO<sub>2</sub> resulted in a substantial increase in ionic conductivity, especially in the more highly ordered solid phases of the material, and also stabilised the most ordered phase to lower temperatures. <br>