The calix[4] arene Mannich base was synthesized and characterized by nuclear magnetic resonance. The electrochemical behavior of compound a ₁（An acidic salt of the calix[4] arene Mannich base (dimethylamine)）and compound b ₁（An acidic salt of calix[4] arene Mannich base (diethylamine)）was studied by cyclic voltammetry, single potential step time current method, time keeping method and conventional pulse polarography (voltammetry) with CH ₃COOH—CH ₃COONa as buffer solution. The result shows that there is an irreversible oxidation peak in a scan potential of -0.5 V to 1.5 V. The oxidation peak potentials are 0.92 V and 0.89 V respectively. The peak current and peak potential of the oxidation peak are linear with the scanning rate. The formation of oxidation peak is controlled by diffusion. The activation energy of the reaction is 11.62 kJ/mol and 13.35 kJ/mol respectively.