The preparation and characterization of the crystalline inclusion complexes between a polymeric guest, poly(1,3-dioxolane) (PDXL), and small-molecular hosts, cyclodextrins (CDs) are reported. It is observed that the polymer guest can form crystalline inclusion complexes with three kinds of cyclodextrins, which may be attributed to the high oxygen atom density in PDXL chain. The crystalline inclusion complexes were characterized with FTIR , TGA, X-ray diffraction, SEM, 1H NMR and 13C CP/MAS NMR spectroscopes. It was found that the crystalline inclusion complexes have higher temperature stability than the pure CDs. The X-ray powder diffraction patterns of the crystalline inclusion complexes proved that they have columnar structures. 13C CP/MAS NMR spectra of the crystalline inclusion complexes indicate that CDs adopt a more symmetrical conformation in the complexes, while pure CDs assume a less symmetrical conformation in the crystal without a guest inside their cavities. The morphology of the crystal was The preparation and characterization of the crystalline inclusion complexes between a polymeric guest, poly (1,3-dioxolane) (PDXL), and small-molecular hosts, cyclodextrins (CDs) are reported. complexes with three kinds of cyclodextrins, which may be attributed to the high oxygen atom density in PDXL chain. The tethered inclusion complexes were characterized with FTIR, TGA, X-ray diffraction, SEM, 1H NMR and 13C CP / MAS NMR spectroscopes. It was found that the crystalline inclusion complexes have higher temperature stability than the pure CDs. The X-ray powder diffraction patterns of the crystalline inclusion assemblies proved that they have columnar structures. 13C CP / MAS NMR spectra of the crystalline inclusion complexes indicate that CDs adopt a more symmetrical conformation in the complexes, while pure CDs assume a less symmetrical conformation in the crystal without a guest inside their cavities. The morphology of the crystal was