A convenient general method is described for the isolation of optically active ruthenium(II) complexes, cis-[Ru(phen) 2X 2] n+ . The resolution strategy involves the initial preparation of the Δ and Λ isomers of cis-[Ru(phen) 2(CH 3CN) 2](PF 6) 2. These precursor compounds were characterized by UV-Vis, 1H NMR and CD spectral analysis, while enantiomeric purity was verified by conversion to optically active [Ru(phen) 3] 2+. Subsequent nucleophilic displacement of both coordinated CH 3CN by X − (where X − = CN −, Cl −, py) proceeds with near complete retention of configuration. The isolation of the optically active neutral species cis-[Ru(phen) 2(CN) 2] and cis-[Ru(phen) 2Cl 2] is significant, since the traditional resolution method via diastereoisomer formation is not directly applicable. Furthermore, cis-[Ru(phen) 2(CN) 2] may serve as a valuable chiral building block for an extensive series of polymetallic complexes where CN − functions as a bridging ligand. The availability of authentic samples of resolved cis-[Ru(phen) 2Cl 2] is important for the quantitative assessment of stereoselectivity in the covalent binding of such racemic complexes with DNA.