Photoresponsive nanoporous polymer films have been fabricated by adding a photoresponsive azobenzene cross-linker to a hydrogen-bonded smectic liquid crystalline polymer network. A base treatment resulted in the nanoporous material which has been fully characterized. Upon exposure to UV light a decrease in the smectic layer spacing is observed, suggesting a decrease in pore size. In addition, the binding sites in the material could be changed with light, leading to light-induced adsorption of cations and cationic dyes. Finally, light could also be used to create nanoporous channels in the polymer film.