Volatile Organic Compounds (VOCs) are toxic for the environment and human health and their tendency to readily volatilize in the atmosphere can lead to problems connected to odours annoyance. Conventional VOCs gaseous emissions treatments entail the application of chemical-physical processes, only promoting the transfer of the contaminants from gas to liquid and/or solid phases. Advanced Oxidation Process (AOPs) and biological processes, conversely, support the oxidation of the organic pollutants, promoting their conversion into harmless and odourless compounds. The integration of booth processes is suggested to increase treatability of VOC. The research presents the application of an innovative treatment system composed by an AOPs pretreatment coupled with a bio-scrubbing unit for the abatement of VOCs, with the aim to increase the removal efficiency. The evaluation of the performance of the proposed system is discussed with reference to the analysis carried out using toluene as model substance. Different operating conditions have been analyzed and investigated to optimize the removal efficiency. The results show that the ozonation applied as pretreatment to the biological process may promote an increase of the pollutant biodegradability along with synergic effects due to the absorption of the ozone derived compounds into the culture growth, resulting in a significant enhancement of removal performances respect to the conventional biotechnologies. A toluene removal efficiency up to 95% were obtained under the investigated conditions.