A new oxovanadium(V) complex of NH4VO3 and tryptophan (TrpH) has been synthesized in aqueous solution at pH 6.0 and characterized by elemental analysis, UV-Vis, FT-IR. H-1-NMR and mass spectroscopic data. The complex (Na-4[V3O9(Trp)]) was diamagnetic in nature as was evident from the electron spin resonance spectroscopy (ESR) and the magnetic susceptibility measurements, in conformity with the presence of vanadium(V) in the structure. The electrochemical behaviour of Na-4[V3O9(Trp)] complex was also studied on the hanging mercury drop electrode (HMDE) by using cyclic voltammetry (CV). The cyclic voltammograms of Na-4[V3O9(Trp)] complex exhibit two new reduction waves at -0.38 V and -1.01 V in Britton-Robinson buffer (pH 6.0) for the potential range from 0.0 V to -1.2 V.