The prerequisite for cellulosic biochemical production from lignocellulosic materials is efficient enzymatic hydrolysis that is a complicated heterogeneous catalytic process and affected by the complex lignin-cellulose-hemicellulose network. Understanding the main influencing factors for enzymatic hydrolysis is of substantial significance to guide the design of a biorefinery process. An experimental study of the pretreatment indicated that acid pretreatment is preferable for herbaceous feedstocks. Therefore, the classic dilute sulfuric acid pretreatment was utilized to hydrolyze and remove hemicellulose from three representative types of agricultural straws at various intensities. From the enzymatic hydrolysis of residual cellulose perspective, the crystallinity index and enzyme accessibility of the pretreated materials were also mathematically correlated to hemicellulose removals, respectively. For the better insight and understanding of the mathematical logics, the linear and nonlinear kinetic models were therefore compared, and the relationship was established by the five-parameter logistic equations and Allosteric sigmoidal models with well fittings.