Two oxoperoxovanadium(V) complexes, [VO(O2)(BHA)(bp)] (1) and [VO(O2)(BHA)(phen)] (2), containing benzhydroxamic acid (BHA), 1,10-phenanthroline (phen) and 2,2’-bipyridyl (bp) ligands are synthesized and the structure of the complexes have been confirmed by single-crystal X-ray crystallography. The DNA-binding studies of the complexes as assessed by UV absorption and fluorescence methods using CT-DNA suggest the possible mode of interaction as groove binding. The gel electrophoresis further supports the feasible interactions of complexes with DNA. The binding constants (Kb) and Stern-Volmer (KSV) constants of 1 and 2 are 5.4(±0.21)×104 M−1 and 5.1(±0.10)×104 M−1 and 5.668(±0.08)×105 M−1 and 1.468(±0.07)×105 M−1, respectively. © 2020, © 2020 Informa UK Limited, trading as Taylor & Francis Group.