Hydrogen-bonded frameworks (HOFs) with permanent microporosity are still hard to obtain, due to the inherent nature of easy-to-collapse of HOF skeleton on solvent removal. On the other hand, tuning the electronic structure of HOFs by incorporating redox-active units for expanding the functionality of this class of material presents a waiting-for unveiled and highly desired field. In this work, the redox-active imide unit was utilized to construct HOF. The resultant HOF (namely ECUT-HOF-30) enables robust microporous structure of ca. 4.0 Å, performing effective separation of C₂H₂/CO₂ via the unique molecular recognition from imide oxygen atoms. Whilst exciting optoelectronic active properties such as photochromism and electrochromism were observed in this HOF. The proof-of-concept results open up a gate for fundamental design of advanced HOFs with redox-active unit and versatility.