A new V(IV) complex, [VO(naph-ser)(phen)]center dot 1.5CH(3)OH (naph-ser = Schiff base derived from l-serine and 2-hydroxy-1-naphthaldehyde, phen = 1,10-phenanthroline), has been synthesized and characterized by single crystal X-ray diffraction. The V(IV) atom is six-coordinated in a distorted octahedral environment. In the crystal of the complex, a 2D network is formed via intermolecular hydrogen bonds. The DNA-binding properties of the complex have been investigated by spectroscopic methods and viscosity measurements. The results indicate that the complex can bind to calf thymus DNA in a non-classical intercalative mode with a binding constant K (b) of 6.83 x 10(3) M-1 and a weak electrostatic attraction. The interactions between the complex and bovine serum albumin (BSA) have also been studied by spectroscopic methods, showing that the complex can interact with BSA and induce conformational changes in the protein. The calculated apparent binding constant K (b) was 4.22 x 10(6) M-1.