Ligno-cellulosic biomass from different sources presents very variable compositions. Consequently, there is a wide variation in the nature and quantities of gaseous products obtained after thermal treatment of biomasses. The objective of this work is to establish a link between the composition of a biomass and its pyrolysis gas yields and composition. Experimental flash pyrolysis of several biomasses at a temperature of 950 degrees C and a gas residence time of about 2 s was carried out. An attempt was then made to predict gas yields of any biomass according to its composition. We show that an additivity law does not allow the gas yields of a biomass to be correlated with its fractions of cellulose, hemicellulose and lignin. Several potential explanations are then offered and quantitatively demonstrated: it is shown that interactions occur between compounds and that mineral matter influences the pyrolysis process. (C) 2008 Elsevier Ltd. All rights reserved.