The present study reports on the formation of supramolecular fibers from a novel cyclen-based ligand and metal salts. In particular, the fibers were shown to stabilize supramolecular porous materials of low density. It was also demonstrated that these fibers could be functionalized by radical polymer growth on their surface. Such new supramolecular fibers constitute a simple and tunable starting material for the synthesis of 1D core-shell objects.