Coordination polymers containing different metal ions and ligands have been widely studied in materials science and synthetic chemistry. For constructing a coordination polymer, the most useful method is to employ an appropriate bridging ligand. Many multidentate ligands bind to two metal ions in two different directions, which shows bridging capability via simultaneous ligations. In our study, we have selected N'1-((E)-2-hydroxybenzylidene)-N'2-(2-hydroxybenzylidene)oxalohydrazide (L), which is a multidentate ligand that can bind to metal ions from more than one donor’s atom. In the first step, the coordination polymers were prepared by reacting the ligand with vanadium acetylacetonate, which yielded a dioxidovanadium(V) complex. In the second step, dioxidovanadium(V) complex was then reacted with sodium carbonate in ethanol solution, resulting in the formation of the one-dimensional vanadium(V) coordination polymer. A novel one-dimensional metal-based coordination polymer of the composition [VNaO₆C₁₁H₁₄N₃]­_n was characterized by IR and NMR and the structure was established by single-crystal X-ray crystallography. The coordination sphere of the vanadium atom is square pyramidal and chelates to a tridentate (-ONO-) ligand, while the square pyramidal conformation of the sodium atom consists of one bridging oxygen atom link to the vanadium atom and the ligand which coordinates in a bidentate fashion. The coordination polymer showed very selective homogeneous catalytic activity with 80-96% conversion in oxidative bromination of the organic substrate under mild conditions.