To apply gliding arc discharge (GAD) plasma processing to volatile organic compounds (VOCs) emission control, the formation of NO(2) as an undesired byproduct needs to be addressed. Comparative results of effluent temperature and product concentrations between experiment and thermodynamic equilibrium calculation show that the NO(2) formation in dry air GAD is totally out of thermodynamic equilibrium. Meanwhile, obvious NO (A(2)Sigma+)) and N(2)(+) (B(2)Sigma(u)(+)) are detected as the major reactive species in the dry air GAD plasma region. These results suggest that the thermal (or Zeldovich) NO(x) formation mechanism is not significant in GAD system, while the energy level and the density of electrons in the plasma region will severely influence the NO(2) formation. The presence of 500 ppm VOCs in the feed gases shows a limiting influence on the NO(2) formation, which is in the order of aromatic hydrocarbon (C(6)H(6) and C(7)H(8))>straight-chain hydrocarbon (C(4)H(10) and C(6)H(14))>halogenated hydrocarbon (CCl(4)). The influences of VOCs chemical structure, supply voltage, feed gas humidity, and reactor geometry on NO(2) formation are investigated, and the results correspond to above mechanism analysis. Based on the above, the possible pathways of the inhibition of NO(2) formation in GAD-assisted VOCs decomposition process are discussed.