The influence of temperature (100–150°C) and acid concentration (0–5 wt%) on the prehydrolysis of pine bark and its alkaline-extracted residues was studied (the latter were obtained by vigorously stirring the bark for 15 min with a solid/liquid ratio of 1:10). Optimal prehydrolysis conditions were established by the sectioning method with a solid/liquid ratio of 1:10. For milled bark these conditions were: temperature 125°C, sulphuric acid concentration 2 wt%, duration of prehydrolysis 4.5 h; and for alkali-extracted residues, temperature 125°C, sulphuric acid concentration 3 wt%, duration of prehydrolysis 5 h. These treatments removed respectively 90% and 75% of non-glucose sugars in the hydrolysate while solubilizing less than 20% (respectively 10%) of the potential glucose yield. Enzymatic digestion of bark successively alkali-extracted and prehydrolysed under optimal conditions gave poor results, with yields similar to those obtained after other pretreatments.