A gold electrode modified with adsorbed thionine monolayer was investigated with ac impedance and cyclic voltammetry method. It was found there were some different redox properties for the adsorbed thionine depended on the different potential scanning rate. At the slower potential scanning rate (10 mV·s -1 ), the dimer of thionine appeared and possessed the catalytic activity for the oxidation of ascorbic acid. The underpotential deposition (UPD) and the bulk deposition of Cu 2+ were also employed to investigate the monolayer of adsorbed thionine.