Placing fluorine atoms at selected positions allows enantiopure hexacoordinate phosphate anions to behave as effective chiral solvating and resolving agents for RuII complexes (the structure of one of the anions is shown: F: yellow; O: red; Cl: green; P: purple). The structural features of the asymmetric ion pairing can be determined by NMR spectroscopy owing to the presence of the fluorine atoms.