Steam explosion (SE) pretreatment is an efficient technique to promote the fiber degradation and disrupt materials' cell wall. In this study, the effect of SE pretreatment on the changes in phenolic profile, and the in vitro digestion property of a Chinese indigenous herb “Hangbaiju” (HBJ) powder with various sieve fractions (150‐, 180‐, 250‐, 425‐, and 850‐μm sieves) were studied. After SE pretreatment, the morphological structure, color attributes, and composition of phenolic compounds were altered significantly (p < .05). The composition and content of phenolic compounds were strongly correlated with particle sizes. The higher extraction yield of phenolic compounds was reached in the intermediate sieve fraction (ca. 250‐μm sieves). During in vitro digestion, the changes in phenolic compounds were significant due to the transition from an acidic to the alkaline environment (p < .05). Based on the multivariate statistical analysis, apigenin‐7‐O‐glucoside, luteolin‐7‐O‐glucoside, and linarin, were viewed as the characteristic compounds among various samples. The results highlighted that the phytochemical properties mainly including the composition of phenolic compounds, and in vitro digestion properties of HBJ powder with intermediate sieve fraction could be improved after SE pretreatment.