Industrial waste gas emissions from fossil fuel over‐exploitation have aroused great attention in modern society. Recently, metal‐organic frameworks (MOFs) have been developed in the capture and catalytic conversion of industrial exhaust gases such as SO2, H2S, NOx, CO2, CO, etc. Based on these resourceful conversion applications, in this review, we summarize the crucial role of the surface, interface, and structure optimization of MOFs for performance enhancement. The main points include (1) adsorption enhancement of target molecules by surface functional modification, (2) promotion of catalytic reaction kinetics through enhanced coupling in interfaces, and (3) adaptive matching of guest molecules by structural and pore size modulation. We expect that this review will provide valuable references and illumination for the design and development of MOF and related materials with excellent exhaust gas treatment performance.