Heterogeneous reactions associated with porous solid films are ubiquitous and play an important role in both nature and industrial processes. However, due to the no-slip boundary condition in pressure-driven flows, the interfacial mass transfer between the porous solid surface and the environment is largely limited to slow molecular diffusion, which severely hinders the enhancement of heterogeneous reaction kinetics. Herein, we report a hierarchical-structure-accelerated interfacial dynamic strategy to improve interfacial gas transfer on hierarchical conductive metal-organic framework (c-MOF) films. Hierarchicalc-MOF films are synthesized via the in-situ transformation of insulating MOF film precursors usingπ-conjugated ligands and comprise both a nanoporous shell and hollow inner voids. The introduction of hollow structures in thec-MOF films enables an increase of gas permeability, thus enhancing the motion velocity of gas molecules toward thec-MOF film surface, which is more than 8.0-fold higher than that of bulk-type film. Thec-MOF film-based chemiresistive sensor exhibits a faster response towards ammonia than other reported chemiresistive ammonia sensors at room temperature and a response speed 10 times faster than that of the bulk-type film.