Six supramolecular polypseudorotaxanes (2-7) like the missing link have been constructed by coordination of the β-cyclodextrin/4,4'-dipyridine inclusion complex (1) with cobalt chloride, cobalt acetate, cobalt nitrate, zinc chloride, zinc acetate, and zinc nitrate, respectively, and investigated using 1H NMR spectroscopy, circular dichroism, FT-IR, gel permeation chromatography, powder X-ray diffraction, thermogravimetric and differential thermal analysis, transmission electron microscopy, and cyclic voltammetry. The obtained results indicate that polypseudorotaxanes 2-7 could self-assemble to form square or rodlike nanostructures. The counteranions play critical roles in the formation of the polypseudorotaxane nanoarchitectures. Especially polypseudorotaxane 2 shows better electrochemical property as compared with that of other polypseudorotaxanes 3-7, which may potentially be used as an electroactive soft material.