A specially designed photo-catalytic electrode-incorporated-dielectric barrier discharge (DBD) reactor has been used to investigate the interaction between photo-catalytic electrode and DBD. Toluene conversion by oxidation was enhanced dramatically due to the synergy between DBD and photo-catalytic electrode. The photo-catalytic electrode could be fully activated in the non-thermal plasma at high peak voltages without extra UV light source. Peak voltage, initial concentration, residence time and humidity were important factors that influenced the toluene conversion. 160 mg/m(3) toluene conversion reached 89.9% at a peak voltage of 40 kV and with a residence time of 4 s in the reactor photo-catalytic electrode. Photo-catalytic electrode could improve DBD system's water-resistance by turning more water molecules into OH radicals. And it also made the reactor have better performance in mineralization rate and CO2 selectivity. (C) 2015 Elsevier B.V. All rights reserved.