A liquid-crystalline (LC) monomer containing a bis(azobenzene)-based metallomacrocycle was synthesized and found to form a columnar hexagonal (Col(H)) LC phase. Adding solvent to swell the cross-linked Col(H) phase allows the azobenzene macrocycles to undergo photo-isomerization from the "closed" to "open" form with retention of LC order to afford a supramolecular polymer with photo-responsive nanopores.