This paper describes the effects of electrode configuration and the loading amount of Ag catalyst on the decomposition of gas-phase benzene using plasma-driven catalyst (PDC) reactors. Modification of ground electrode brought out a great enhancement in the energy efficiency for benzene decomposition by reducing abnormal discharges outside the reactor tube. The data of carbon balance and the selectivity of CO2 indicated that the Ag catalyst played an important role in the decomposition of benzene, especially for the intermediates. The larger the Ag-loading amounts on the TiO2, the better the performance of benzene decomposition in terms of the carbon balance and the selectivity of CO2. Formation of NO2 and N2O indicated that the maximum specific input energy applicable to the PDC reactor should be determined not only by the decomposition efficiency but also by the formation of nitrogen oxides.