Using the organic ionic plastic crystal N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C2mpyr][FSI]) with electrospun nanofibers, LiFSI doped [C2mpyr][FSI]-PVdF composites were developed as solid state, self-standing electrolyte membranes. Different lithium salt concentration were investigated, with 10 mol% LiFSI found to be optimal amongst those assessed. Composites with different weight ratios of plastic crystal and polymer were prepared and 10 wt% polymer gave the highest conductivity. In addition, the effects of PVdF incorporation on the morphological, thermal, and structural properties of the organic ionic plastic crystal were investigated. Ion mobilities were also studied using solid-state nuclear magnetic resonance techniques. The electrolytes were then assembled into lithium symmetric cells and cycled galvanostatically at 0.13 mA cm-2 at both ambient temperature and at 50°C, for more than 500 cycles.