Utilizing environmentally-friendly bacterial cellulose as a scaffold, a highly porous, layered OA-BC catalyst was synthesized through an enhanced sol-gel process. This catalyst demonstrated exceptional performance in the oxidation of toluene, outperforming conventional alternatives that utilize chemical porogens. The OA-BC catalyst efficiently degrades toluene at 220℃ with high stability and hydrophobicity, indicating resistance to deactivation. Its superior activity is due to increased oxygen vacancies, enhanced metal oxide cooperation, and a layered porous structure, which together enhance active oxygen species and oxygen diffusion. Calcination of the OA-BC catalyst results in molecular cleavage and formation of small aggregates, increasing hydroxyl groups that stabilize Cu and Ce centers, enhancing toluene-oxygen reactions. In-situ infrared and X-ray photoelectron spectroscopy confirm stable monodentate Cu+ ligands, contributing to its high catalytic activity. This study introduces a novel approach by employing bacterial cellulose as a template for synthesizing a porous stratified OA-BC catalyst, demonstrating superior performance in toluene oxidation. The efficacy of catalyst results from a tripartite synergy involving the stratified porous architecture, the stabilizing effect of Cu+-coordinating ligands and hydroxyl groups, and the interplay of hydroxyl electron donors and acceptors, shedding light on environmentally benign catalyst development.