A method for the chemical modulation of the photoluminescence of a DNA-bound diruthenium(II) complex, [(bipy) 2 Ru(bpib)Ru(bipy) 2 ] 4? (bipy = 2,2 0 -bipyridine, bpib = 1,4-bis([1, 10]phenanthroline [5,6-d]imidazol-2-yl) benzene) by the introduction of Cu 2? ion and EDTA has been developed. The diruthenium(II) complex showed strong photoluminescence both in buffer solutions and on an indium-tin oxide (ITO) surface, which was not modulated by Cu 2? or EDTA. The DNA-bound [(bipy) 2 Ru(bpib)Ru (bipy) 2 ] 4? with a binding constant of 3.8 9 10 4 M -1 showed an enhancement in the luminescence based on the electrostatic interaction between the complex and DNA. The presence of Cu 2? was found to quench the luminescence of DNA-bound [(bipy) 2 Ru(bpib)Ru(bipy) 2 ] 4? , but the quenched luminescence was recovered by addition of an equimolar concentration of EDTA. Hence, the photoluminescence of DNA-bound [(bipy) 2 Ru(bpib)Ru(bipy) 2 ] 4? depends strongly on the introduction of Cu 2? and EDTA.