The leather waste generated by the footwear industry is considered dangerous due to the presence of trivalent chromium, derived from the salt utilized to tan hides. In Brazil, the majority of this waste is disposed on landfills and only about 3% are recycled. The thermal treatment is an alternative method for purification of such residues. By using this technique it is possible to generate energy and recover the chromium present in the ash for the production of basic chromium sulfate (tanning industry), high carbon ferrochromium or carbon-free ferrochromium (steel industry). In the last 10 years, the gasification and combustion of footwear leather waste have been intensively studied at the Federal University of Rio Grande do Sul. The research experiment for characterization of the emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were carried out in a semi-pilot unit (350 kW(th)). From new investments the thermal capacity of the unit will increase to 600 kW,h. The unit will produce power from the heat generated in the combustion. The experimental results indicated that during the thermal treatment of footwear leather wastes, the formation mechanism of PCDD/F is the de novo synthesis. Most of PCDD/F were found in the particulate phase (>95%). A kinetic model was used for discussion of the achieved experimental results. The model is based in the carbon gasification, PCDD/F formation, desorption and degradation. From the conclusions obtained in this work will be possible minimize the PCDD/F formation in process of combustion of footwear leather wastes. (C) 2009 Published by Elsevier B.V.