Synthesis, characterization, and catalytic properties for styrene epoxidation of a new oxovanadium(V) complex [VOLL′] · CH3OH (I) derived from N′-(3-bromo-5-chloro-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H2L) and benzohydroxamic acid (HL′) are reported. Complex I was characterized by elemental analyses, IR, UV-Vis spectra and molar conductivity. Single crystal X-ray structure of complex I has been determined (CIF file CCDC no. 1034615). The V atom in the structure is in an octahedral coordination. In the crystal structure, molecules are linked through intermolecular O-H⋯O, O-H⋯Br and N-H⋯O hydrogen bonds, to form 2D layers. Catalytic property for epoxidation of styrene by the complex using PhIO and NaOCl as oxidant has been studied.