Nanometer-sized supramolecular assemblies created by the simple inclusion complexation of host cyclodextrins (CDs) and guest molecules have attracted more and more attention in recent years because of their potential to serve as molecular devices and molecular machines, as well as functional materials. [1-4] Indeed, CDs can be threaded on a polymer chain to form a polyrotaxane and extended to molecular tubes through the cross-linking of adjacent CD units in a polyrotaxane.[5] Furthermore, b- and g-cyclodextrins can also be constructed into nanometer-sized molecular tubes linked by diphenylhexatrienes,[6] and conjugated polyrotaxanes can be used as building blocks to form insulated molecular wires on which a- or b-CDs are threaded.[7] We recently showed that the resulting complex formed from an organoseleniumbridged b-CD dimer and a platinum ion could be fabricated into bis(molecular tube)s through formation of a pesudorotaxane with poly(propylene glycol), and the bridged bis(bcyclodextrin) s and calix[4]arene derivatives could also form nanometer-sized linear aggregations by simple host-guest inclusion complexation.[8-10] Molecular semiconductors can also be exploited for organic electronics and single molecules can be manipulated and incorporated into nano-engineered devices at a supramolecular level by threading a chargetransport macromolecule.[11-15] However, higher order polymeric rotaxanes fabricated by metal-ion binding to the inclusion complexes formed between CDs and aromatic molecules have not been investigated so far. Dipyridine-metal complexes have very interesting photochemical and other properties, and therefore many studies have been devoted to this topic.[16] Herein we report our investigations on two uncommon supramolecular aggregations: assembly 1, formed from the reaction of b-CD with 4,4'-dipyridine (DPD), and polymeric rotaxane 2, which was synthesized by coordination of 1 with NiII ions. The binding behavior of 1 and 2 was examined, both in solution and in the solid state, by 1H NMR spectroscopy, X-ray crystallography, induced circular dichroism, powder X-ray diffraction studies, thermogravimetric (TG) and differential thermal analysis (DTA), scanning tunneling microscopy (STM), and transmission electron microscopy (TEM). The binding behavior of the supramolecular assembly formed by the molecular recognition of the host and guest in solution and in the solid state is of particular interest, since the inclusion complex and the polymeric rotaxane display different photophysical behavior. The present investigations have revealed that the resulting complex of CDs with guest molecules is the first step in the formation of a polymeric rotaxane, which provides access to coordination polymeric supramolecules with CDs, and will serve to further our understanding of this developing, but less investigated, area of electroactive organic materials that contain CDs and a coordination linkage.