This study evaluated the organosolv pretreatment with crude glycerol as a cosolvent for the delignification of raw sugarcane bagasse and the release of fermentable sugars from enriched-cellulose fraction by enzymatic hydrolysis. The pretreated solid fractions were characterized by pulp yield, weight loss, cellulose and hemicellulose content, lignin content, and delignification extent. Condition 9 (210 ºC, 60 min, 8 mL g-1) led to the highest delignification (~79%) with high total reducing sugars (TRS) concentration (~300 g L-1) and lower carbohydrate preservation (< 41%). While condition 1 (180 ºC, 150 min, 8 mL g-1) led to the highest cellulose preservation (~70%) and TRS (> 412 g L-1), even with a lower delignification extent (> 69%). This work contributed to an effective and optimized strategy to reuse crude glycerol in organosolv pretreatment as a facilitator of lignocellulose delignification, in addition to validating new protocols for the biorefinery production chain, providing sustainable biomaterials with added value.