This study proposed an integrated technique of reduction coupled with an oxidation process in order to acquire simultaneously both decolorization and mineralization of orange II under the condition of microwave-assisted milling. Experimental variables of initial dye concentration, iron dosage, microwave power, solution pH and initial H2O2 concentration were systematically studied. Under the optimal operational parameters (100 mg/L aqueous solution of pH 3 containing 400 mg/L H2O2 while controlling microwave power at 400 W), the results showed that the decolorization efficiency is up to 91% after reaction for 2 min and the total organic carbon removal efficiencies were 72.7% and 80.5% at a reaction time of 10 min and 60 min, respectively. It indicated that the decolorization and mineralization of orange II were largely enhanced by the reduction of zero-valent iron in the ball milling process and the oxidation of hydroxyl radicals generated by hydrogen peroxide. It suggested that microwave-assisted ball milling technology has potential application for degradation of azo dye in wastewater.