Electrochemical behavior of a series of halogenated acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, alpha-bromopropionic acid, 2-bromobutyric acid, and 4-bromobutyric acid at C-60-octasodium calix[8]aryloxy octakis-(propane-3-sulphonate) (represented as C-60-L) and Nafion chemically modified electrodes in mixed acetonitrile and water (3:2, v:v) was investigated systematically and comparatively by cyclic voltammetry. It was found that C-60-L/Nafion is capable of mediating the electron transfer to alpha-halogenated organic acid, showing it could be used to catalytically reduce the above organohalide compounds, except for 4-bromobutyric acid. Values of the rate constant, k, for the electrocatalytic dehalogenation of monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid by C-60-L anion were determined by using the rotating-disk electrode voltammetry.