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Glycerol-plasticized high-amylose corn starch/konjac glucomannan (HCS/KGM) composite films incorporated with various concentrations of β-cyclodextrin (β-CD) were prepared and investigated for structural, mechanical, and physical properties. The results of X-ray diffraction, attenuated total reflectance Fourier transform infrared spectroscopy, thermogravimetric analyses, and scanning electron microscopy indicated that β-CD excluded from the polymer chains and aggregated to form crystals during film formation, which drove HCS to interact with KGM more compactly. The thickness and transparency of the films increased after β-CD was incorporated. More associations of HCS/KGM enhanced the mechanical properties and reduced the moisture content of the films. The water vapor permeability of the HCS/KGM composite film was also improved significantly with the incorporation of β-CD. The enhanced association between biopolymers in the presence of β-CD will advance the development of a degradable active composite packaging film.