Thermal decomposition of volatile organic compounds (VOCs) such as n-hexane and toluene has been studied in an inductively coupled thermal plasma reactor, at atmospheric pressure, in neutral and oxidative conditions, respectively. Thermodynamic calculations were performed for predicting the product distribution due to thermal decomposition. Based on these calculations formation of the products observed in the gas phase and in the extract of soot could be interpreted. In neutral conditions formation of soot and PAH was detected to different extent for the different models. The presence of oxygen in the plasma reactor depresses both soot and PAH formation. GC-MS analyses of the gaseous products and the extract of the soot, respectively, refer to as complex decomposition and recombination mechanism in given conditions.