Efficient and high yield production of xylooligosaccharides, arabinooligosaccharide and mannooligosaccharides from biomasses is a significant boost to the nutraceutical and pharmaceutical industry. These organic compounds, also known as prebiotics, promote the growth of intestinal probiotic microorganisms thus improving the hosts' overall immune system. This work aimed at designing a thermochemical pretreatment of biomasses leading to production of high prebiotic yields and assessing the liquor quality based on resultant oligomer-monomer constituents. Four biomasses, namely Miscanthus sinensis, Panicum virgatum, Calamagrostis acutiflora and Bagasse, each having a dry weight xylan content of >= 20% were used. Identification and quantification using HPLC and ion chromatography systems showed xylooligomer yields of 65.0%, 84.2%, 87.9% and 92.3%, respectively. The xylooligomers also showed a degree of polymerization ranging from 2 to 25. These results demonstrate the potential of a low cost, pretreatment process of biomasses which may be suitable for a commercial scale production of prebiotics. Published by Elsevier Ltd.