Acid red B (ARB) solution with pH = 3 was electrolyzed in a two-chamber cell using Pt/C gas diffusion electrode (GDE) as cathode. The color and COD removal ratio in cathode chamber were 94.2% and 66.8% respectively; and the color and COD removal ratio in anode chamber were 73.3% and 56.6% respectively, which indicated that O2 can be reduced to H2O2 and x OH in the cathode chamber, then ARB was degraded. Through IR and GC-MS analysis for the intermediates of ARB in the cathode chamber, 20 intermediates have been detected, including 14 esters, 3 acids and 3 compounds with -NO2 or N-OH groups and the probable degradation pathway of ARB in the cathode chamber was given.