Equilibrium thermochemical calculations of polystyrene are presented here under conditions of pyrolysis and oxidative pyrolysis. Oxidative pyrolysis is examined using both air and oxygen for varying moisture content in the polystyrene. The pyrolysis of polystyrene at different temperatures prior to its oxidative pyrolysis provided significantly different results. Product gas volume and flame temperature is significantly affected by the pyrolysis temperature, nature and amount of the oxidant and the amount of moisture in the waste. Results reveal significant effect of controlled combustion on the amount and nature of the chemical species formed. The results also reveal that advanced combustion process can significantly reduce the extent of post processing of gases required, and hence the size of the equipment, for achieving environmentally acceptable thermal destruction system of the solid wastes.