A microwave/Fe3O4 catalytic system was proposed for treatment of volatile organic carbons (VOCs). This system comprises a household microwave oven modified as the reaction chamber, which was fitted with a vertical, cylindrical quartz reactor comprising a catalytic packed column filled with granular Fe3O4, a microwave catalyst of iron (II, III) oxide. Experimental results showed that the destruction and removal efficiency (DRE) of toluene by microwave alone was close to zero, but with the microwave/Fe3O4 system, the temperature of the catalytic packed column increased rapidly and reached thermal balance within 10-15 min. Analysis of the rear gas after combustion showed that most of the toluene was thermal oxidized into CO2 and H2O. The successful application of the proposed microwave/Fe3O4 system to thermal destruction of toluene promises a new technology for treatment of VOCs.