Thermal analysis, impedance spectroscopy, NMR and Raman spectroscopy have been used to investigate the plastic crystal dimethylpyrrolidinium thiocyanate in order to gain further insight into the properties of organic ionic plastic crystals. This compound has a solid-solid phase transition at 82 degrees C, and melts at 122 degrees C. A step increase in conductivity of about one order of magnitude is observed at the phase transition, followed by a decrease in activation energy for conduction. A large entropy gain occurs at the H -> I transition, and H-1 NMR linewidth measurements together with second moment calculations showed that the dimethylpyrrolidinium. cation goes from a static state, to full isotropic tumbling. Raman measurements confirm that the cation as well as the anion exhibit increased rotational mobility when entering phase I. (C) 2008 Published by Elsevier B.V.