Electrochemical oxidation of Acid Red 3R (AR3R) was investigated with the new catalyst of iron phosphomolybdate (FePMo12) supported on modified molecular sieves type 4 Å (4A) as packing materials in the reactor. The results of the Fourier transform infrared spectroscopy and X-ray diffraction indicated that the heteropolyanion had a Keggin structure. The optimal conditions for decolorization of simulated AR3R wastewater were as follows: current density 35 mA/cm2, initial pH 4.0, airflow 0.08 m3/hour and inter-electrode distance 3.0 cm. With the addition of NaCl to the system, the decolorization efficiency increased. But Na2SO4 had a negative effect on the decolorization efficiency, which was attributed to the negative salt effect. The degradation mechanisms of AR3R were also discussed in detail.