Hemicellulose, an amorphous biopolymer of pentoses and hexoses sugars, accounts for about 25- 28% of the biomasses, to say roughly 40% of the total carbohydrates, and this implies the importance of effectively converting it to value added products. Hemicellulose is easier to hydrolyse than cellulose and the dominants sugars are mannose (six-carbon sugars) in softwoods and xylose (five-carbon sugars) in hardwoods and agriculture residues. Biorefineries for the production of second generation bioethanol are already in the demonstration step and the processes layouts mostly involve the simultaneous conversion of six-carbon sugars (C6) and five-carbon sugars (C5) to ethanol by using genetically modified microorganisms. Despite the noticeable advances on the recovery and conversion of hemicellulose carbohydrates, this subject remains challenging because an efficient process needs to satisfy various conditions, namely the selection of a suitable pretreatment which reduces the thermal degradation of the hemicellulose sugars, the enhancement of the soluble olygomers hydrolysis since they could inhibit the cellulose enzymatic hydrolysis in a simultaneous process, the effective conversion of the monomers to value added products. The present paper compares various options to convert the Arundo donax derived hemicellulose to biofuels (bioethanol, and butanol) and chemicals (furfural). Acid-catalysed steam explosion was used for the biomass pretreatment and fractionation. Hemicellulose-derived xylose was dehydrated to furfural in biphasic media by microwave energy in presence of solid acid catalysts. The results indicate that, at optimized fermentation conditions, xylose was converted to ethanol by Scheffersomyces stipitis with 70% yields whereas the maximum achieved furfural yield was 48%. In these conditions, the energy efficiency of the two process options were similar.