The aim of this kinetic work is to provide a better understanding of the pyrolysis of lignin and biomasses not only in terms of devolatilazation rate but also of the volatile species released. The complexity of both lignin structure and its degradation mechanism meant that a lumping approach suitable for handling the huge amount of initial, intermediate and final products had to be used. Despite these simplifications, the proposed semi-detailed kinetic scheme involves about 100 molecular and radical species in 500 elementary and lumped reactions. It has already been proved that this lignin devolatilization model correctly predicts the degradation rates and the detail of the released products. This work constitutes an initial yet significant step towards deriving a complete kinetic scheme of biomass devolatilization. (C) 2009 Elsevier Ltd. All rights reserved.