A comparative study of the decomposition of Volatile Organic Compounds (VOCs: Vinyl Chloride (VC), Ethyl Acetate (EA), Toluene (T), Acetone (A)) in dielectric barrier discharges (DBD) in zero and humidified air at atmospheric pressure was performed. Small scale tubular-flow with pulse excitation and large scale planar-flow with sinusoidal excitation were used to determine the removal efficiency in dependence on inlet concentration S-0 and air humidity. According to the destruction law S=S-0 exp(-E/beta), where E is the plasma energy density, linear functions were found for the beta-parameters with respect to S-0 containing an absolute term beta(0). By modeling the reaction kinetics it was possible to discriminate active species responsible for the decomposition. Ozone was confirmed to be involved in VC decomposition in zero air whereas OH radicals were best suited to explain the absolute efficiency of EA and toluene destruction in humid air. Their decomposition in zero air however, as well as the degradation of acetone cannot be explained in a similar way.