Using scanning tunneling microscopy (STM), electrospray ionization mass spectrometry (ESI-MS), and X-ray photoelectron spectroscopy (XPS), we demonstrate that a free (2]catenane consisting of two interlocking 30-membered rings (cat-30) can be deposited on a Ag(111) surface by vacuum sublimation without decomposition. The deposited cat-30 molecules self-organize as ordered dimer chain structures at the surface, presumably via intermolecular pi-pi stacking. An in situ addition of Cu atoms to the surface-adsorbed catenanes induces a drastic change in the molecular organization, i.e., from the dimer chain structure to isolated species. The nitrogen core level spectra suggest that the cat-30 phenanthroline units coordinate with Cu, indicating that the free catenane has been transformed into a Cu-complexed [2]catenane. Since it is known that the two interlocked macrocyclic rings of the free ligand cat-30 completely rearrange, i.e., circumrotate, upon complexation to copper, our results reveal that when adsorbed on the silver surface, the two macrocyclic rings of the free [2]catenane can glide within one another so as to generate the corresponding copper complex by in situ Cu complexation.