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Complex characteristics of p-sulfonated calix[4]arene (SC4A) and colchicine were examined using various techniques. Electrochemical impedance spectroscopy results enabled observation of the colchicine-SC4A interaction, and indicated that SC4A had high sensitivity to colchicine with a detection limit (S/N = 3) of 2 × 10-9 mol L-1. Cyclic voltammetry results indicated that the structural matching effect and the electrostatic interaction were the dominant stabilizing factors for the host-guest complexes of colchicine and SC4A. Molecular mechanics simulation showed that the benzene ring of colchicine entered the SC4A cavity. The sensor enabled selective determination of colchicine even in the presence of common interferences. The results indicated that it was more difficult to oxidize the non-electrochemically active complexes. This study showed that p-sulfonated calix[4]arene can be used in the detoxification of colchicine poisoning and may be effective in the clinical treatment of colchicine poisoning in the future.