The potential of fast-growing poplar species was evaluated for bioethanol production. The yields of glucose and xylose from acid and enzymatic hydrolysis were compared. The hydrolysis processes were performed on raw and extracted wood. The extracted wood was obtained by action of a chloroform and 96% ethanol (93:7 w/w) mixture. Additionally, to enhance the enzymatic hydrolysis efficiency, a liquid hot water (LHW) pretreatment was used. The acid hydrolysis turned out to be a good method to verify the biomass potential for bioethanol production. After acid hydrolysis of raw and extracted biomass, high total sugars yields were obtained (between 626.2 to 808.5 mg/g raw or extracted biomass), while in the case of enzymatic hydrolysis the total sugars yields were very low (between 45.5 to 68.9 mg/g raw or extracted biomass). The LHW pretreatment greatly enhanced the enzymatic digestibility of the studied wood. The average glucose yield from enzymatic hydrolysis was up to 602.0 mg/g pretreated biomass and was higher than that from acid hydrolysis (the maximum yield was 566.9 mg/g extracted biomass). As a result of the LHW pretreatment, up to 91.3% of the hemicelluloses were removed from the solid fraction. From the obtained glucose and xylose results, it was concluded that Populus trichocarpa wood had a higher potential for bioethanol production than P. deltoides x maximowiczii wood. The presence of extractives (low molecular substances) in raw poplar wood (up to 2.8%) had a low impact on the yield from acid and enzymatic hydrolysis.