In conclusion, highly efficient SO₂/CO₂ separation has been achieved by HOF-NKU-1 through GA and SM effect. The storage density of SO₂, selectivity, and dynamic capture of SO₂ at high humidity conditions exceeds the reported benchmark materials. In addition, HOF-NKU-1 can be recycled and reused through simple recrystallization, resulting in significant material cost savings. Therefore, this work not only provides a new direction for the gas separation and storage, but also provides a basis for the discovery of more HOF materials with other functions in the future. Future research can focus on: (1) validation of the large-scale synthesis, long-term cycling stability, and economics; (2) developing dynamic in-situ characterization techniques to reveal the molecular mechanisms of the GA effect; (3) exploring the versatility of HOFs in the separation of other acidic gases (such as NO_x). The emergence of such flexible porous materials may provide a new paradigm for the next generation of green chemical technologies.