A method to pretreatment of biomasses using glycerol as a green solvent was developed. Optimization of organosolv pretreatment was performed using a 23 factorial design, investigating synergism among the variables particle size (from < 0.85 to > 2.0 mm), FeCl3 concentration (0.025-0.175 mol L-1), and temperature (160-220 °C). Although the effects of the variables differed according to the type of lignocellulose, it was nonetheless possible to find an optimal condition in common (< 0.85 mm; 0.025 mol L-1; 220 °C), which was economically and environmentally sustainable, employing a small amount of catalyst. The biomasses pretreated using this combination of factors exhibited enzymatic digestibility exceeding 93% after 48 h, reflecting efficient reduction of recalcitrance as a result of high removal of hemicellulose (ca. 90%), provided by the use of FeCl3, together with substantial delignification. There was low formation of inhibitors in the hydrolysate, indicating that it could be directly fermented. The lignin removed to liquors could be easily recovered by centrifugation. Tests carried out under the optimal condition revealed that after the pretreatment the biomass could be directly used in enzymatic hydrolysis, without washing and wet. Furthermore, after simple treatment, crude glycerol was as effective as commercial glycerol.