The lanthanide(III) complexes of general formula of [Ln(BPBH)₂(NO₃)₃] (where, Ln = La, Ce, Pr, Nd and BPBH = 2-benzoylpyridine benzhydrazone) have been synthesized and characterized by elemental analysis, molar conductance, spectroscopic (UV, IR), electrochemical and single crystal X-ray diffraction studies. The coordination mode of the ligand and the geometry of [Ce(BPBH)₂(NO₃)₃] are confirmed by single crystal X-ray studies. The crystals are monoclinic with C2/c crystallographic symmetry. The central metal is 12 coordinated and the coordination polyhedron around the cerium atom can be described as a distorted icosahedron. The existence of nitrate. . . 𝜋 and CH. . . 𝜋 stacking interactions in the [Ce(BPBH)₂(NO₃)₃] leads to a supramolecular arrangement in its network. The binding properties of these complexes with calf-thymus DNA have been investigated by viscosity measurements. The complexes show more nuclease activity in the presences of H₂O₂.