Platinum filament pyrolyzers achieve very high temperature and heating rate and can provide useful parameters for practical applications in combustion, pyrolysis and gasification processes. The critical use of an experimental instrument is necessary to provide reliable data. In this work, a commercial pyrolyzer (CDS Pyroprobe 2000) is characterized to obtain a correspondence between the nominal and the effective operating conditions. This is the basis for the modeling estimation of the effective thermal history of the sample during each experimental run. The experimental results obtained performing the devolatilization of coals, biomass and waste fuels using the pyrolyzer are compared with those obtained in a conventional thermogravimetric balance, to evaluate the effects of extremely different operating conditions. The amount of volatile released programming the most severe thermal conditions using the pyrolyzer (thus in conditions more similar to large-scale plants) differs significantly from that of thermogravimetric runs. Global kinetics are obtained fitting the experimental results and using the thermal history of the sample from the model results. They depend strongly on the conditions used for the devolatilization. Global kinetics obtained in the thermogravimetric balance runs (low heating rate) overestimate the rate of devolatilization in the pyrolyzer (high heating rate). (c) 2006 Elsevier Ltd. All rights reserved.