Biorefinery of sugarcane bagasse into ethanol and xylitol was investigated in this study. Ethanol fermentation of sugarcane bagasse hydrolysate was carried out by Saccharomyces cerevisiae. After ethanol distillation, the vinasse containing xylose was used to produce xylitol through fermentation by Candida guilliermondii TISTR 5068. During the ethanol fermentation, it was not necessary to supplement a nitrogen source to the hydrolysate. Approximately 50 g/L of bioethanol was produced after 36 h of fermentation. The vinasse was successfully used to produce xylitol. Supplementing the vinasse with 1 g/L of yeast extract improved xylitol production 1.4-fold. Cultivating the yeast with 10% controlled dissolved oxygen resulted in the best xylitol production and yields of 10.2 ± 1.12 g/L and 0.74 ± 0.04 g/g after 60 h fermentation. Supplementing the vinasse with low fraction of molasses to improve xylitol production did not yield a positive result. The supplementation caused decreases of up to 34% in xylitol production rate, 24% in concentration, and 24% in yield.