The detoxification of soil and sludge from polychlorinated dibenzo-dioxins (PCDD) and -furans (PCDF) has been achieved by means of the K-PEG technology based on the in situ formation of the complex between polyethylene glycol (PEG) and KOH. Dechlorination of the pollutants was promoted by heating the samples up to 250 degrees C, above the PEG thermal degradation onset (>140 degrees C). As a consequence, a bursting evolution of hydrogen was observed which gave a reductive character to the reaction media and atmosphere. PCDD and PCDF chlorine atoms were progressively eliminated by a hydrodehalogenation reaction. After optimisation of the experimental parameters, the toxicity index was lowered more than 98%. In order to gain insight on the mechanism of the reaction, PEG thermal degradation chemistry was studied in some detail. The analytical results (mainly by mass and IR spectroscopy) suggest that PEG has an essential role on promoting the dehalogenation reaction by acting as a phase transfer agent as well as a source of hydride.