1H, (19)F and (31)P pulsed field gradient spin-echo (PGSE) diffusion studies on chiral organic salts that contain hexacoordinate phosphate anions, namely tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) and bis(tetrachlorobenzenediolato)mono([1,1']binaphthalenyl-2,2'diolato)-phosphate(V) (BINPHAT), are reported. The first example of the dependence of a diffusion value on diastereomeric structure is presented. Marked solvent and concentration effects on the diffusion constants (D) of these salts are noted and the question of ion pairing is discussed.