HOFs are a class of crystalline porous materials with predictable topologies and tunable structures. They have been initially hindered by relatively weak hydrogen-bonding interactions, as many HOFs collapse upon guest solvent removal. Recently, designing constructors with large π-conjugated systems to form intermolecular shape-fitting π-π stacking interactions can greatly enhance the thermal stability of HOFs. More importantly, these HOFs with large π-conjugated structures can accelerate electron transfer when redox reactions occur due to the overlapping steric orbital interactions.