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We have recently reported a series of thiophene-containing ruthenium(Ⅱ)complexes [1-4].Here we report on the two Ru(Ⅱ)complexes of [Ru(Htip)3]2+ 1 and [Ru(Htip)2(dppz)]2+ 2.The ground-and excited-state acid-base properties of 1 and 2 were studied and demonstrated that 1 acted as a pH-induced “on-off-on” luminescence switch.The binding behaviours of 1 and 2 to calf thymus DNA were studied with absorption and emission spectroscopy,DNA viscosities and density functional theory calculations.2 was found to act as a DNA molecular light switch and as an efficient photocleaver of pUC 18 DNA.The cytotoxicity of the complexes were evaluated with the MTT method,and it was found that 1 displayed selective anticancer activity against MCF-7 cells whereas 2 exhibited moderate activities against all cancer cell lines tested.