In this paper, the influence of physicochemical pretreatment methods on the chemical composition, enzymatic hydrolysis efficiency and porosity of fast-growing Populus trichocarpa wood was compared. Among the pretreatment methods, the liquid hot water (LHW) and steam explosion (SE) were used, which were performed at three different temperatures (160 °C, 175 °C and 190 °C) and two residence times (15 min and 1 h). The chemical composition, enzymatic hydrolysis and porosity analysis were done for native wood and solid fraction obtained after LHW and SE pretreatments. The porosity analysis was performed by inverse size exclusion chromatography method. Additionally, inhibitors of hydrolysis and fermentation processes in the liquid and solid fractions obtained after pretreatments were examined. Based on the results, it was found that the tested pretreatments caused the greatest changes in the chemical content of hemicelluloses. It was found that after LHW and SE pretreatments up to 99.1% or 94.0%, respectively, of hemicelluloses were removed from the obtained solid fraction. Moreover, the LHW and SE processes greatly enhanced the enzymatic digestibility of fast-growing poplar wood. The highest glucose yield was achieved after 15 min of SE pretreatment at 190 °C and was 676.4 mg/g pretreated biomass, while in the case of xylose the highest value (119.3 mg/g pretreated biomass) was obtained after 15 min of LHW pretreatment at 160 °C. Generally, after SE pretreatment process, more inhibitors were formed, and a greater effect of porous structure development was noticed than after LHW pretreatment. Despite this difference, the average glucose contents and yields after enzymatic hydrolysis of pretreated biomass were generally similar regardless of the pretreatment used.