Supported phosphotungstic acid catalysts on gamma-Al2O3 (HPW/gamma-Al2O3) were prepared by solution impregnation and characterized by FTIR, XRD, TG-DTA and SEM. The heteropolyanion shows a Keggin structure. Electro-chemical oxidation of Acid Red 3R was investigated in the presence of HPW supported on gamma-Al2O3 as packing materials in the reactor. The results show that HPW/gamma-Al2O3 has a good catalytic activity for decolorization of Acid Red 3R. When HPW loading was 4.6%, pH value of Acid Red 3R was 3, the voltage was 25.0 V, air-flow was 0.04 m3 x h(-1), and electrode span was 3.0 cm, the decolorization efficiency of Acid Red 3R can reach 97.6%. The removal rate of color had still about 80% in this electro-chemical oxidation system, after HPW/gamma-Al2O3 was used for 10 times, but active component loss existed. The interim product was analyzed by means of Vis-UV absorption spectrum. It shows that the conjugated structure of dye is destroyed primarily.