In the manufacturing of cellulose derivatives, improving cellulose accessibility is essential for achieving a high product quality. In this study, endoglucanase enzyme treatment was applied prior to the cationization reaction to enhance the accessibility of hydroxyl groups for the production of cationized dialdehyde cellulose (CDAC). A range of enzyme dosages (0.09–45.00 ECU/g) was tested, and their effects on the swelling behavior and surface charge density of the final product were evaluated. The surface charge density of the ultimate cellulosic derivative confirmed its cationization and was proven to enhance the charge density of cationized dialdehyde cellulose (35% increase) compared to untreated pulp with enzyme. Additionally, the modified cellulose exhibited a significantly higher swelling capacity than regular pulps. These findings suggest that enzymatic pretreatment can enhance fiber reactivity and support a more sustainable and efficient production of cellulose-based derivatives, offering a promising potential for commercial applications.