The synthesis of Cu(II) and Ni(II) complexes with thiosemicarbazone(L) ligand and their characterization have been reported in our previous research paper, J. Chem. Pharm. Res., 2011, 3(5):682-688. By this research work we tried to monitor UV-VIS spectral and structural changes accompanying electron transfer, the electrochemical properties of metal complexes particularly with sulphur donor atoms have been studied. The polarograph measurements were made on the degassed (all solution) was deoxygenated by passing nitrogen into DMF(dimethyl formamide) solution (10-3 M) for 10 minutes prior to the recording of polarograms. Solution (10- 2 M) containing TEAFB (Tetraethyl ammonium fluroborate) was used as the supporting electrolyte. The three-electrode system consisting of drooping mercury (working), platinum wire (counter) and K/KCI (reference electrodes).