The utilization of coal-based activated carbons focuses on improving the physicochemical structure for achieving high-capacity. Herein, the catalytic effect of NaCl (1 and 3 wt%) in the presence of oxygen functional groups on the improvement of the physicochemical structure of coal-based activated carbons is studied in this work. A large quantity of Na can be retained in 1NaJXO and 3NaJXO with the presence of oxygen functional groups to promote further its catalytic characteristics during pyrolysis, resulting in the disordered transformation of the carbon structure. In addition, the development of micropores is mainly affected by the distribution and movement of Na catalyst, whereas the growth of mesopores is mainly influenced by the evolution of oxygen functional groups. Then, the active sites of 3NaJXO-800 can no longer be consumed preferentially in the presence of Na catalyst during subsequent CO2 activation to facilitate the sustained disordered conversion of the microstructure and the rapid development of the micropores, resulting in the obvious high SBET value as activation proceeds. And the high SBET/burn-off ratio value (41.48 m2∙g−1/%) of 3NaJXO-800 with a high value of SBET (1995.35 m2∙g−1) at a low burn-off value (48.1%) can be obtained, presenting the high efficiency of pore formation. Finally, the SO2 adsorption efficiency of 3NaJXO-800-48.1 maintains at 100% within 90 min. After 180 min, 3NaJXO-800-48.1 still presents a high adsorptive capacity (140.2 mg/g). It is observed that a large micropore volume in the case of hierarchical pore structure necessarily assures optimal adsorption of SO2.