Nano-catalyst was prepared in the lab. Non-thermal plasma was generated by dielectric barrier discharge (DBD). Through nano-catalyst coupled with non-thermal plasma, a series of experiments for toluene decomposition were carried out. Based on reactor input energy density and removal efficiency and energy efficiency and inhibition for O3 formation, the load amount MnOx catalyst on the surface of γ-Al2O3 pellets were compared in the experiment. The results show the catalysis performance of 10 wt% MnOx/γ-Al2O3 coupled with non-thermal plasma resulted in higher removal efficiency of toluene and better energy efficiency. At the same time, 10 wt% MnOx/γ-Al2O3 operated on a better inhibition for O3 formation in the gas exhaust.