Volatile organic compounds (VOCs) are typical pollutants that affect the air quality. Discharge plasma is thought to be a potential method that can remove VOCs from flue gas. In this experiment, pulsed corona discharge plasma combined with biological tower was carried out to remove benzene series, and toluene was selected as the typical VOCs. Results indicated that the removal efficiency of toluene by pulsed corona plasma was slightly higher than that of direct current (DC) corona plasma, while its energy efficiency was much higher than DC corona plasma. Under the optimal experimental conditions of pulse voltage 8.5 kV, initial toluene concentration 1400 mg/m3 and toluene flow rate of 12 L/h, the toluene removal efficiency reached 77.11% by the single method of pulsed corona discharge plasma, and the energy efficiency was up to 1.515 g/(kW∙h) under the pulse voltage of 4.0 kV. The trickling biofilter was constructed by using the screened and domesticated Acinetobacter baumannii, and the highest toluene removal efficiency by the pulsed corona discharge plasma combined with trickling biofilter rose up to 97.84%. Part of toluene was degraded into CO2, H2O and some intermediate products such as o-diphenol under the action of Acinetobacter baumannii. When the remaining waste gas passed through the discharge plasma reactor, the benzene ring structure could be directly destroyed by the collision between toluene and plasma. Meanwhile, O·, OH· and some other oxidizing radicals generated by the discharge also joint into the oxidative decomposition of toluene and its intermediate products, thereby further improving the removal efficiency of toluene. Therefore, the two-stage plasma-biofilter system not only showed a high toluene removal efficiency, but also had a good energy efficiency. Results of this study would provide a theoretical support and technical reference for industrial VOCs treatment.