Abstract The pyrolysis behaviors of several agricultural residues have been investigated by using thermogravimetric analysis. The evolving rates of the gaseous products during the pyrolysis such as H 2, CH 4, H 2O, CO and CO 2 were also measured by the TG-MS techniques. Without any assumption and mathematical fitting, we could obtain the very proper kinetic parameters (the distribution curve of activation energy, f( E), and the activation energy dependent frequency factor, k 0( E)) of biomass pyrolysis by utilizing the distributed activation energy model (DAEM) proposed by Miura and Maki [Miura K, Maki T. Energ Fuel 1998;12:864]. The peaks of f( E) curve for rice straw, rice husk, corncob and cellulose were found to be 170, 174, 183, and 185 kJ/mol, respectively. The k 0 value increased from an order of 10 11 to an order of 10 18 s −1, while E increased from 120 to 250 kJ/mol. The catalytic effects of alkali and alkaline earth metals during the pyrolysis play a major role in the variation of f( E) curve among the different biomass species.