A straightforward method for the synthesis of virtually enantiomerically pure ruthenium(II) polypyridyl complexes [Ru(pp)(pp')(pp '')](PF6)(2), pp = bidentate polypyridyl has been developed. The synthesis draws from the readily available racemic starting material cis-[Ru(pp)(pp')Cl-2] and the natural amino acids L- or D-proline and relies on a dynamic asymmetric transformation under thermodynamic control.