The supramolecular polypseudorotaxane (3) with π-conjugated polyazomethine is directly synthesized by the polycondensation of two simple inclusion complexes of β-cyclodextrin/o-tolidine (1) and β-cyclodextrin/p-phthaldehyde (2) and is comprehensively characterized by NMR, FTIR, circular dichroism spectra, powder X-ray diffraction, thermogravimetric (TG) and differential thermal analysis (DTA), scanning electron icroscopy (SEM), and scanning tunneling microscopy (STM) both in solution and in the solid state. The results obtained have revealed linear microstructure of polypseudorotaxane 3 and different photophysical behavior as compared with the ð-conjugated polyazomethine backbone (4). The present investigations prove a simple method for preparing supramolecular polypseudorotaxane by different complexes, which possess the potential to serve as molecular devices/machines and optical materials.