To solve the problems of complex equipment and low removal efficiency of VOCs with plasma coupled catalysts. In this study, toluene was used as a substitute for VOCs, and MnO₂/CeO₂ composite catalyst was directly electrodeposited on corona discharge anode to form a catalytic film, and the effective coupling of plasma and catalyst was achieved, which reduced the complexity of the equipment and ensured the high efficiency of toluene cracking. The results show that the oxygen concentration is beneficial to improve the catalytic activity of the catalyst but reduces the corona discharge plasma intensity. When the oxygen content is 5.5% and the voltage is 12 kV, the highest cracked rate of toluene can reach 95%. MnO₂ has strong high voltage resistance and can prolong the effective catalytic time of the catalyst. CeO₂ has high catalytic activity, mainly for the complete removal of toluene fragments. When the concentration of Ce³⁺ in the electrodeposition solution is 0.02 mol/L and the electrodeposition time of MnO₂ is 60 min, the ratio of MnO₂ to CeO₂ in the MnO₂/CeO₂ composite catalyst is the best, and the cracked rate of toluene is the best. Finally, the plasma discharge in this system and the mechanism of toluene removal by catalyst coupled plasma are analyzed in detail.