From the prospective of possible electrochemical application of vanadium complexes, here, we report the two novel vanadium complexes. Namely, Tp*VO(3,5-Me2pzH)2(CH3CN) (1) (where, Tp* = hydro tris(3,5-dimethylpyrazolyl)borate and Tp*VTp*(2) these complexes were prepared in a good yield starting from V(III) chloride and hydro tris (3, 5 dimethyl pyrazolyl) borate. Both the complexes were characterized by NMR, Mass, and FTIR spectroscopy. In addition, cyclic voltammetry is used to investigate electrochemical processes of 1 and 2. The electrochemical active species exhibits two noteworthy redox peaks and exhibits considerable catalytic action towards glassy carbon electrodes with a composite of multi-walled carbon nanotubes (MWCNTs). Moreover, the complex1/MWCNTs/GC electrode detects the H2O2 in PBS (pH 7) electrolyte solution by cyclic voltametry (CA), differential pulse voltametry (DPV) and chronoamperometry (CA) techniques; Under the optimal conditions, the reduction peak current is linear to the H2O2 concentration in the ranges, detection limit for; CA: 50–500 μmol; 4.5 μmol L−1, CV: 50–400 μmol; 9.5 μmol L−1, DPV: 50–500 μmol; 8.3 μmol L−1. Single-crystal XRD analysis revealed that complex 1 crystallized in the orthorhombic space group P212121with lattice parameters a = 11.960(4) Å, b = 12.571(4) Å, c = 20.465(7)Å, Z = 4. In addition, distorted octahedral geometry was observed around the vanadium metal centre. Surface morphology of the complexes was probed by scanning electron microscopy (SEM).