A polystyrene-[Ni2+]-poly(ethylene oxide) metallo-supramolecular block copolymer (PS-[Ni2+]-PEO), where -[is a terpyridine, is used to create nanoporous thin films with free terpyridine ligands homogenously distributed on the pore walls. The PS-[Ni2+]-PEO block copolymer is synthesized by a two step assembly process, and is then self-assembled into a thin film in order to obtain PEO cylinders oriented perpendicularly to the film surface. The supramolecular junction is opened by exposing the film to an excess of a competing ligand, and the free PEO block is then rinsed away by a selective solvent. The presence of the terpyridines on the pore walls is evidenced by fluorescence spectroscopy after formation of a fluorescent complex with an europium salt.