Electrochemical behavior of C-60-octasodium calix[8]aryloxy octakis-(propane-3-sulphonate) complex in Nafion films (represented as C-60-L/Nafion) on electrodes was studied by cyclic voltammetry (CV) in mixed solvent of acetonitrile and water containing alkali-metal salts or tetra-butylammonium perchlorate (TBAP) as supporting electrolyte. Two reduction peaks and one oxidation peak were obtained in a mixed solvent of acetonitrile and water (3:2, v:v) using TBAP. The charge transfer (CT) reaction in the complex results in a negative shift of the peak potential of the first cathodic peak compared with the reduction of a pure C-60 film. It was also found that C-60-L is capable of mediating the electron transfer to chloroacetic acid, promoting its electrocatalytic reduction.