Self-assembled monolayers of shape-persistent macrocycles have been adsorbed on highly orientedpyrolytic graphite and Au(111) substrates. Their structure and binding characteristics have been investigatedby scanning tunneling microscopy, X-ray photoelectron spectroscopy, and ultraviolet photoelectronspectroscopy experiments. Special functionalization of the macrocycles for the first time has enabled theirself-assembling and binding on a metal substrate and opened a new route for new functional nanostructures.