The effect of the H2SO4 concentration in the hydrolysis of sunflower‐stalk waste, at 95ºC and using a liquid/solid relation of 20, was studied. In a later stage, the hydrolysates were fermented at different temperatures with the aim of ethanol and xylitol production. A total conversion of the hemicellulose at the acid concentration of 0.5 mol/L was achieved; whereas an acid concentration of 2.5 mol/L was needed to reach the maximum value in the conversion of the cellulose fraction. The analysis of the hydrolysis kinetics has enabled to determine the apparent reaction order, which was 1.3. The hydrolysates from hydrolysis process with H2SO4 0.5 mol/L, once detoxified, were fermented at pH 5.5, temperatures 30, 40, and 50ºC with the yeast Hansenula polymorpha (ATCC 34438), resulting in a sequential uptake of sugars. In relation to ethanol and xylitol yields, the best results were observed at 50°C (YE/sO = 0.11 g/g; YXy/sO = 0.12 g/g). Instantaneous xylitol yields were higher than in ethanol, at the three temperatures essayed. Different phenolic compounds were analyzed in the hydrolysates; hydroxytyrosol was the most abundant (3.79 mg/L). The recovery of these compounds entails the elimination of inhibitors in the fermentation process and the production of high value‐added antioxidant products.