Abstract: A one-dimensional {[Cu(phen)(azpy)(NO3)(H2O)]·(NO3)}n coordination polymer (1), where azpy = 4,4′-azopyridine and phen = 1,10-phenanthroline, has been synthesized and characterized by elemental anal., FT-IR and UV-Visible spectroscopy, thermal anal. and single crystal X-ray diffraction (SCXRD).The SCXRD shows that compound (1) forms a zig-zag, one-dimensional (1D) coordination polymer through the bridging azpy spacer.The 1D polymer chains self-assemble to form a three-dimensional network through hydrogen-bonding, π-π stacking and ion-dipole interactions.The N4O2 coordination sphere of copper(II) involves two nitrogens from different azpy′s, two nitrogens from phen, one oxygen from water and one oxygen from a nitrate anion.Thermal studies reveal that the coordination polymer (1) is thermally stable upto 166 °C.Compound (1) cleaves plasmid pBR322 DNA by an oxidative mechanism involving hydroxyl and superoxide radicals at low concentrationsGraphical Abstract: A one-dimensional {[Cu(phen)(azpy)(NO3)(H2O)]·(NO3)}n coordination polymer (1), where azpy = 4,4′-azopyridine and phen = 1,10-phenanthroline, has been synthesized, characterized and plasmid pBR322 DNA cleavage activity has been investigated. [graphic not available: see fulltext]