In this study, a novel multilayer cathode composite of ACF@rGO@OMC (ACF = activated, carbon fibers, rGO = reduced graphene oxide, and OMC = ordered mesoporous carbon) with high electrical conductivity was successfully prepared. Transmission electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry results show that the ACF@rGO@OMC composite possesses excellent properties of ordered mesoporous structure, high specific surface area, high electroactive surface area, and lower impedance. When this fabricated ACF@rGO@OMC composite electrode is applied, the reduction of oxygen to generate hydrogen peroxide was promoted from 31 to 85 mg.L-1 and the current efficiency of the electro-Fenton process was also improved from 25.0% to 40.0%. The yield of (OH)-O-center dot had increased obviously. The ACF@rGO@OMC composite applied for removal of phthalic acid esters using an electro-Fenton process, and it remained stable after reacting 10 times.