The electrochemical degradation of acid red B (ARB) with hydrogen peroxide and hypochlorite ion electrogenerated by paired electrooxidation technology was investigated. High performance liquid chromatography (HPLC) was used to inspect the degradation process of ARB. Through analyzing chromatographic survey and UV-Vis spectra, as well as the removal of CODCr, TOC and color in the anode and cathode cells, the degradation processes of ARB in different cells were different. The color removal in the cathode cell was slower than in the anode cell, but the CODCr and TOC removal, which were 71.70% and 56.40% respectively, was higher than the removal in the anode cell, which were 25.15% and 27.57%. It maybe result from the different oxidation capabilities of the electrogenerated substances in the anode and cathode cells.