The pyrolysis mechanism of hemicellulose has been investigated using two minimally damaged hemicellulose polymers isolated from two agricultural straw samples. The obtained hemicelluloses have been characterized by multiple methods, and the results showed that they were mainly composed of L-arabino-4-O-methyl-D-glucurono-D-xylan. Their O-acetyl groups and high degrees of polymerization and branching were well preserved. Their pyrolyses were subsequently investigated by TG-FTIR and Py-GC/MS. The evolutions of four typical volatile components and the distributions of eight product species were scrutinized. A DG-DAEM kinetic model was applied to quantify the contributions of two major pyrolytic routes for devolatilization during hemicellulose pyrolysis. A mean activation energy of 150 kJ/mol for the formation of volatiles was derived. The thermal stability of each bond in four typical fragments of hemicellulose was assessed by DFT study, and the deduced decomposition pathways were in agreement with experimental analysis. (C) 2015 Elsevier Ltd. All rights reserved.