In this work, hemp (Cannabis sativa L.) stalks were pretreated with pyrrolidinium acetate [Pyrr][AC] to increase the availability of cellulose for cellulolytic enzymes and thus improve the production of 2G ethanol from reducing sugars. The process was carried out under different temperature and time conditions: The control sample was raw material and deionized water, and the second sample was kept at 21 °C for 24 h. The third sample was kept at 90 °C for 30 min, and the fourth sample was kept at the same temperature for 24 h. For each pretreatment, the extraction of lignin and hemicellulose was determined, as well as the change in biomass composition before and after pretreatment. The stalks of hemp seed contained 41.54% cellulose, 18.08% lignin and 28. 87% hemicellulose. [Pyrr][AC] used to dissolve seed hemp at 90 °C for 24 h was most effective in the extraction of this biopolymer, extracting 3.1% content. After enzymatic hydrolysis, the highest content of reducing sugars was found for samples of hemp stalks that were first pretreated with proton ionic liquid (PIL) and stirred at 90 °C for 24 h. On the other hand, the highest ethanol content (5.6 g/L) after fermentation and yeast viability (56.7%) after 72 h were obtained in samples pretreated at 90 °C and for 24 h.