Laboratory-scale experiments were performed to evaluate the humidity effect on toluene decomposition by using a wire-plate dielectric barrier discharge (DBD) reactor at room temperature and atmospheric pressure. The toluene decomposition efficiency as well as the carbon dioxide selectivity with/without water in a gas stream of N2 with 5% O2 was investigated. Under the optimal humidity of 0.2% the characteristics of toluene decomposition in various background gas, including air, N2 with 500 ppm O2, and N2 with 5% O2 were observed. In addition, the influence of a catalyst on the decomposition was studied at selected humidities. It was found that the optimum toluene removal efficiency was achieved by the gas stream containing 0.2% H2O, since the presence of water enhanced the CO2 selectivity. In addition, the toluene removal efficiency increased significantly in a dry gas stream but decreased with an increase in the humidity when the Co3O4/Al2O3/nickel foam catalyst was introduced into the discharge area.