The redox behavior of ammonium metavanadate NH₄VO₃ alone and on the interaction with Geimsa Stain and Pyrazole derivative via cyclic voltammetry (CV) has been studied. 0.1M H₃PO₄ was used as supporting electrolyte and NH₄VO₃ as source for +5 vanadium ions. The cyclic voltammograms gave a quasi-reversible redox couple pattern for +5 to +4 vanadium ions in phosphoric acid medium. The redox behavior of ammonium metavanadate (NH₄VO₃) was studied by the interaction of Geimsa strain and pyrazole as ligand forming complexes in 0.1 M phosphoric acid. The study indicated that vanadium (+5) is converted to vanadium (+3) via two steps on using potential window range from 1.5Vto -1.5 V (vs./AgCl/KCl(s)).The thermodynamic parameters, stability constant (k_s) and Gibbs free energies of complexation (∆G_c) resulted from the interaction of NH₄VO₃ with both Geimsa stain and Pyrazole derivative ligands gave better results for the interaction of Geimsa Stain than that in case of pyrazole derivative.