A scalable approach to generating different nanomaterials from the same hydrogen-bondeded complex by photo-crosslinking is described. The hydrogen-bonded complex exhibits a smectic or columnar mesophase, depending on the molar ratio between the donor and acceptor. The mesophase structure is effectively retained after photo-crosslinking. Polymer nanosheets with negatively charged carboxylate groups can be prepared from the complex with the smectic mesophase after subsequent extraction and chemical treatment, and they show effective adsorption of Pd2+. Meanwhile, a nanoporous polymer is successfully achieved from the complex having the columnar mesophase by using the same technology of photo-crosslinking and solvent treatment. This work provides a new strategy to fabricate different nanomaterials from the same hydrogen-bonded complex system.