Transformation of lignocellulosic biomass to biofuels involves multiple processes, in which thermal decomposition, hydrotreatment are the most central steps. Current work focuses on the impact of several solid acids and Keggin-type heteropolyacids on the decomposition temperature (T-d) of pine wood and the characterization of the resulted products. It has been observed that a mechanical mixture of solid acids with pine wood has no influence on T-d, while the use of heteropolyacids lower the T-d by 100 degrees C. Moreover, the treatment of biomass with a catalytic amount of H3PW12O40 leads to formation of three fractions: solid, liquid and gas, which have been investigated by elemental analysis, TGA, FTIR, GC-MS and NMR. The use of heteropolyacid leads, at 300 degrees C, to a selective transformation of more than 50 wt.% of the holocellulose part of the lignocellulosic biomass. Moreover, 60 wt.% of the catalyst H3PW12O40 are recovered. (C) 2013 Elsevier Ltd. All rights reserved.