Synthesis and structural characterization of a new pyridylimidazole based vanadyl compound [VO2(L)(L−)] (1) [L=2-(2-pyridyl)benzimidazole] (1) are reported. It crystallizes in P1¯ space group. The molecular geometry of 1 around vanadium(V) is found to be distorted octahedron. 1 interacts with DNA in a intercalative fashion. Hypochromism of the absorption band of the complex with increasing concentration of DNA and the steady increase in DNA viscosity with increasing concentration of 1 indicates intercalative mode of binding. The binding constant is calculated as 2.76×105M−1. 1 also shows cytotoxicity against human breast cancer, human lung cancer and human keratinocyte cancer cell lines.