Surfaces of fly ashes from three Swedish MSW incinerating plants were extensively characterized to better predict their involvement in the generation of persistent organic pollutants. The ashes were then subjected to thermal treatment at 400 °C in sealed glass ampoules to track the decomposition polychlorinated dibenzo-p-dioxins and furans (PCDD and PCDF). Temperature programmed desorption experiments in the 30-900 °C range also enabled monitoring of thermally decomposing ashes by Fourier Transform Infrared (FTIR) spectroscopy as well as thermally desorbing effluent gases by mass spectrometry. In addition, one ash was doped with (13)C-labelled PCDD and PCDF to evaluate the potential of the experimental setup for elucidating the thermal desorption of the organic molecules. It was found that in ashes with high carbon content PCDD and PCDF decomposition were led pronounced, and that PCDD degraded more readily than PCDF.