AbstractThe effects of structural properties and their changes during cellulose hydrolysis on the enzymatic hydrolysis rate have been studied from the reaction mechanism point of view. Important findings are the following: (1) The crystallinity index (CrI) of partially crystalline cellulose increases as the hydrolysis reaction proceeds, and a significant slowing down of the reaction rate during the enzymatic hydrolysis is, in large part, attributable to this structural change of cellulose substrate. (2) The crystallinity of completely disordered cellulose, like phosphoric‐acid‐treated cellulose, does not change significantly, and a relatively high hydrolysis rate is maintained during hydrolysis. (3) The specific surface area (SSA) of partially crystalline cellulose decreases significantly during enzymatic hydrolysis while the change in SSA of regenerated cellulose is found to be negligible. (4) The value of degree of polymerization (DP) of highly ordered crystalline cellulose remains practically constant whereas the change in DP of disordered regenerated cellulose is found to be very significant. (5) Combination of these structural effects as well as cellulase adsorption, product inhibition, and cellulase deactivation all have important influence on the rate of cellulase reaction during cellulose hydrolysis. More experimental evidence for a two‐phase model, which is based on degradation of cellulose by simultaneous actions of cellulase complex on the crystalline and amorphous phases, has been obtained. Based on experimental results from this study and other results accumulated, the mode of cellulase action and a possible reaction mechanism are proposed.