Agricultural residues represent an abundant, readily available, and inexpensive source of renewable lignocellulosic biomass. However, biomass has complex structural formation that binds cellulose and hemicellulose. This necessitates the initial breakdown of the lignocellulosic matrix. Steam explosion pretreatment was performed on barley straw grind to assist in the deconstruction and disaggregation of the matrix, so as to have access to the cellulose and hemicellulose. The following process and material variables were used: temperature (140-180 degrees C), corresponding saturated pressure (500-1100 kPa), retention time (5-10 min), and mass fraction of water 8-50%. The effect of the pretreatment was assessed through chemical composition analysis. The severity factor R-o, which combines the temperature and time of the hydrolytic process into a single reaction ordinate was determined. To further provide detailed chemical composition of the steam exploded and non-treated biomass, ultimate analysis was performed to quantify the elemental components. Data show that steam explosion resulted in the breakdown of biomass matrix with increase in acid soluble lignin. However, there was a considerable thermal degradation of cellulose and hemicellulose with increase in acid insoluble lignin content. The high degradation of the hemicellulose can be accounted for by its amorphous nature which is easily disrupted by external influences unlike the well-arranged crystalline cellulose. The carbon content of the solid steam exploded product increased at higher temperature and longer residence time, while the hydrogen and oxygen content decreased, and the higher heating value (HHV) increased. (C) 2014 Elsevier Ltd. All rights reserved.