Abstract: Schiff base monomer Ni(salen) and Ni(salphen) with different Imino groups were chemical synthetized and formulated as a solution with the concentration of 1 mmol/L. PolyNi(salen) and polyNi(salphen) were electrodeposited on the prepared MWCNTs electrode through cyclic voltammetry on electrochemical workstation. Surface morphologies of polyNi(salen) and polyNi(salphen) electrodes were characterized by field emission scanning electron microscopy (FESEM) and electrochemical properties were test by cyclic voltammetry, chronoamperometry, galvanostatic charge/discharge methods. Results showed that polyNi(salen) nano-belts were electrodeposited upon MWCNTs, and the polyNi(salphen) were adhesive grown on nanotubes. The charge diffusion coefficients of transition metal complexes polymer polyNi(salen) and polyNi(salphen) electrodes are 12.3×10^-9 cm²/s, 1.86×10^-9 cm²/s, respectively. The specific capacitances of polyNi(salen) and polyNi(salphen) were 66.6 F/g、106.3 F/g at a current density of 0.05 mA/cm², respectively. The capacitance and electrochemical properties of transition metal complexes polymer with tetradentate N₂O₂ Schiff-base ligand polyNi(salphen) is better than of polyNi(salen).