In order to fabricate heterogeneous catalysts based on porous materials, in situ synthesis and post-synthetic modification are two commonly used strategies. However, these strategies usually lead to inaccessible active-sites or pore blocking during the synthesis procedure. Catalysts with interpenetrating porosity and high utilization of active sites in open frameworks are urgently pursued. Porous aromatic frameworks are constructed from building units with designed molecular configuration, so it is possible to achieve specific architecture for pore functionality. Herein we report a strategy to construct “catalytic cavities” within PAF skeletons. Functional groups with catalytic activity are exclusively located in the cavities; therefore the material retains high porosity and full utilization of the active sites. As a result, the obtained catalyst showed wide size tolerance and high efficiency in alcohol oxidation, surpassing the performance of catalysts by post-synthetic modification.