Analysis of N,N-dimethylpyrrolidinium tetrafluoroborate by (1)H and (11)B NMR, Raman spectroscopy and powder XRD shows that this organic ionic plastic crystal material exhibits unusual phase behaviour. (1)H NMR analysis indicates that the mobility of the pyrrolidinium cation decreases when the material is heated into phase I, while the X-ray diffraction pattern changes from a simple, one peak structure in phase II to a more complex pattern in phase I. The possible origins of these unusual transitions are discussed.