Three thermodynamic databases of polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) have been used to simulate the PCDD/F isomer distribution in industrial combustion processes. The three databases had been derived using the Group Additivity approach and two computational molecular modelling methods, Modified Neglect of Diatomic Overlap (MNDO) and Parametrized Model 3 (PM3), respectively. The predictions of the toxic PCDD/F isomer distributions using the three different databases have been compared with measured values from industrial processes. An excellent agreement between the predictions using the MNDO method and the measured data has been obtained. It is concluded that the PCDD/F isomer distributions within each group observed in these combustion processes may be thermodynamically controlled.