A series of ruthenium(II) polypyridine complexes with a crown ether-containing ligand dipyrido[3,2-a:2',3'-c]phenazo-15-crown-5 (dppzc) have been synthesized and characterized and their photophysics and electrochemistry studied. The photoredox reactivities of [Ru(bpy)(2)(dppzc)](2+) have also been investigated by Stern-Volmer quenching experiments and nanosecond transient absorption spectroscopic studies. The cation-binding properties of these ruthenium(II) polypyridine complexes have also been studied by electronic absorption spectroscopy and cyclic voltammetry and confirmed by electrospray ionization mass spectrometry.