Organic ionic plastic crystals (OIPCs) are an emerging family of materials with demonstrated applications in electrochemical devices such as lithium/sodium ion batteries, dye-sensitized solar cells, and hydrogen fuel cells. Herein, we present direct evidence of anion diffusion through a relatively static background of a cation lattice in an ionic plastic crystal compound, [P122i4][PF6], in an elevated temperature solid phase. We found all anions are diffusive, whereas only a small population of cations is diffusive. Two anion populations were identified with diffusion coefficients differing by 2 orders of magnitude. The slow-diffusing anion is attributed to the plastic crystal region where the cation forms a relative static background, allowing anions to diffuse possibly through a defect-assisted hopping mechanism.