Devolatilization behavior of different coals and biomasses under heating conditions typical of conventional pyrolysis processes was investigated. Thermogravimetric analyses were performed on coals (with high and low volatile matter), biomasses (pine sawdust and dried sewage sludge) and coal-biomass blends with different weight ratios. The different behavior of coals and biomass fuels in the devolatilization process (different amount and nature of volatile species released, different rate of devolatilization and different reactivity of produced chars) was analyzed for abstracting kinetic data. In addition, analyses of coal-biomass blends revealed that in the operative conditions used (i.e. low heating rate 20 degreesC/min and high nitrogen flowrate), primary reactions of the thermal decomposition of biomass fuels are not significantly affected by the presence of coal, and also coal does not seem to be influenced by the release of volatile matter from biomass. This led to the first conclusion that the weight loss of a blend can be obtained from the weighted sum of reference materials. Further, a kinetic analysis was performed in order to fit the experimental results and verify simple sub-models (namely, distribution activation energy model and lumped model) to be used in comprehensive combustion codes (computational fluid dynamic) assuring a major accuracy compared with SFOR model, but maintaining both simplicity and computational velocity. A quite good fitting was obtained for all materials and blends studied.