Preliminary xylitol separation tests were carried out using solutions with relativity high concentrations of xylose and xylitol to simulate the actual composition of hemicellulose hydrolyzates. Xylitol was recovered by a crystallization methodology consisting of dilute solution evaporation up to supersaturation, supersaturated solutions cooling, separation of crystals by centrifugation, and final filtration. Two sets of tests were performed on xylitol-xylose synthetic solutions and an additional one on fermented hardwood hemicellulose hydrolyzate. The best results in terms either of crystallization yield (0.56) or purity degree (1.00) were obtained with quite concentrated solutions (730 g/l) at relatively high temperature (-5 degreesC). Besides, xylitol solubility limits in the solution, which are very important for future scale-up of the process, were estimated at different crystallization temperatures. Product yields and crystal purity were calculated and crystallization kinetics were investigated.