New di-and tetranuclear copper(II) complexes of formula [Cu (phen) (mqpa)]·2H2O·CH3CH2OH (1) and [Cu2(phen)2(ppa)2(H2O)2]·4H2O·CH3CH2OH (2) (phen = 1,10- phenanthroline, H2mqpa = 4-(2-methyl-quinolin-1-ium-8-yloxy) phthalic acid, H2ppa = 3-(pyridiium-3-yloxy) phthalic acid) have been synthesized and characterized by elemental analysis, infrared spectrum, and single X-ray diffraction. In complex 1, two [Cu(phen)] units are bridged by two mqpa ligands via carboxyl bridges, forming a binuclear compound with Cu…Cu distance of 3.329 Å. Through strong π…π and CH…π weak interaction, complex 1 molecules are assembled into 2D supramolecular structures. Compound 2 features a metallamacrocyclic assembly in which four [Cu(phen)(H2O)] species are linked together by four ppa bridge ligands in head to tail fashion with Cu…Cu distance of 8.713 and 8.528 Å. The adjacent tetranuclear complex 2 molecules stacked together through strong π…π. The Cu(II) ions in two compounds are all in square pyramidal geometry. The interaction of two complexes with FS-DNA was studied by electronic absorption titration and ethidium bromide displacement experiments, the result displayed both complexes interact with DNA in non-intercalation mode, molecular docking simulation displayed that complex 1 interacts with DNA with a partial intercalation mode and complex 2 favor binding to major groove. Both complexes exhibit cytotoxicity against HeLa cells and AGZY-83a cells, and complex 2 has similar anticancer activity toward HeLa cells with cisplatin. The results of apoptosis assays by flow cytometry shows complex 2 promotes more apoptosis in HeLa cell lines than complex 1.