A novel transition metal coordination polymer [Co3(C14H8NO4Cl)4(CH3OH)4·4CH3OH]n with Schiff base (C14H8NO4Cl: 4-chloroanthranilic acid- 2,4-dihydroxybenzaldehyde) was synthesized using 4-chloroanthranilic acid, 2,4-dihydroxybenzaldehyde and cobalt(II) acetate as source, and its structure was characterized by IR spectroscopy, elemental analysis, 1H NMR and single crystal X-ray diffraction. X-ray crystallography shows that every cobalt atom is six-coordinated. Two cobalt atoms on the two sides are respective coordinated with two nitrogen atoms from –C=N–, two carboxylic oxygen atoms and two hydroxyl oxygen atoms in different ligands, while the cobalt atom in the middle links two ligands on the side through two carboxylic oxygen atoms and coordinates with four oxygen atoms of methanol, forming a three-nuclear Co(II) complex. The complex forms a two-dimensional layer structure through O–H···O intermolecular hydrogen bonds. The interaction of the Co(II) complex with calf-thymus DNA (CT-DNA) was investigated by UV absorption spectroscopy, fluorescence emission spectroscopy, viscosity and cyclic voltammetry. All measurements revealed that the Co(II) complex binds to DNA via a intercalative mode.