Azo dyes discharged in the environment are persistent organic pollutants (POPs),which are very difficult to remove. We developed a microwave-assisted Fenton-like process to degrade methyl orange (MO),an azo dye,with hydrogen peroxide (H2O2) catalyzed by chromium compounds coexisting with MO in the solution. Comparison between the Cr(Ⅲ)-H2O2 and Cr(VI)-H2O2 systems shows that Cr(VI) has a stronger and more stable catalytical activity than Cr(Ⅲ),and Cr(Ⅲ) is more susceptible to a change in the acidity or alkalinity of the reaction system. With a Cr(VI) concentration of 10 mmol L-1 or a Cr(Ⅲ) concentration of 12 mmol L?1 in the solution under the microwave irradiation of a power larger than 300 W for 3 min,10 mmol L-1 H2O2 can degrade more than 95% of 1 000 mg L-1 methyl orange; when the microwave power is increased to 700 W,the same amount of H2O2 can degrade all methyl orange in the solution with the same amount of Cr(VI) catalyst. Ultraviolet-visible spectrography indicates the cleavage of the azo bond in methyl orange after treatment,suggesting the potential of this Fenton-like process to degrade azo dye POPs. Reusing waste chromium compounds coexisting with dyestuff in wastewater to catalyze the degradation of azo dyes could be a cost-effective technique for azo dyes and chromate manufacturers and/or users to treat their wastewater and prevent POPs from endangering the environment. This is of particular importance to controlling the water quality of the Three Gorges Reservoir.