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The combination of chemical oxidation methods with biotechnology to removal recalcitrant VOCs is a promising technology. In this paper, the aim was to identify the role of key process parameters and biodegradability of the degradation products using a dielectric barrier discharge (DBD) reactor, which provided the fundamental data to evaluate the possibilities of the combined system. Effects of various technologic parameters like initial concentration of mixtures, residence time and relative humidity on the decomposition and the degradation products were examined and discussed. It was found that the removal efficiency of mixed VOCs decreased with increasing initial concentration. The removal efficiency reached the maximum value as relative humidity was approximately 40%–60%. Increasing the residence time resulted in increasing the removal efficiency and the order of destruction efficiency of VOCs followed the order styrene > o-xylene. Compared with the single compounds, the removal efficiency of styrene and o-xylene in the mixtures of VOCs decreased significantly and o-xylene decreased more rapidly. The degradation products were analyzed by gas chromatography and gas chromatography-mass spectrometry, and the main compounds detected were O3, COx and benzene ring derivatives. The biodegradability of mixed VOCs was improved and the products had positive effect on biomass during plasma application, and furthermore typical results indicated that the biodegradability and biotoxicity of gaseous pollutant were quite depending on the specific input energy (SIE).