The specific characteristics of biomass structure and chemical composition of straw stem and leaf may result in different behavior of pretreatment and enzymatic hydrolysis. In this work, sodium carbonate (SC) was employed as a pretreatment to improve the enzymatic digestibility of wheat straw. The chemical composition and enzymatic hydrolysis of wheat straw stem and leaf (sheath included) were investigated comparatively. Most of the polysaccharides are kept in the solid fractions after SC pretreatment, while the stem has better delignification selectivity than leaf at high temperature. The enzymatic hydrolysis efficiency of wheat straw leaf is significantly higher than that of stem. The maximum total sugar yield from SC pretreated leaf was about 16% higher than stem. The results show that sodium carbonate is of great potential to be used as a pretreatment for the production of bioethanol from straw handling waste in a straw pulp mill with a low feedstock cost.