Toluene was removed by dielectric barrier discharge coupling with Cu-Ce-Zr supported ZSM-5/TiO2/Al2O3 catalysts. Copper, cerium, and zirconium species were highly dispersed on the support surface, and copper was mostly in Cu2+ and Cu+ state co-existed. The reaction process of toluene removal in the plasma-catalyst system was influenced by the support of the catalyst and it could be divided into three steps. Pure plasma and thermal catalytic chemistry triggered by background temperature played different roles in the different step. Large pore size, more oxygen vacancy and lattice oxygen in the CuCeZr/TiO2 were responsible to the excellent toluene removal, CO2 selectivity and energy yield.