Amylose, which is a helical polysaccharide and well-known as a component of starch, forms controlled assemblies, such as a double helix and inclusion complexes depending on whether guest compounds are present or not. Therefore, amylose has been employed as a functional polymeric material. However, little has been reported regarding the formation of inclusion complexes between amylose and polymeric compounds. The main difficulty in incorporating polymeric compounds into the amylose cavity is that the driving force for the binding is only caused by hydrophobic interactions. Amylose, therefore, does not have sufficient ability to include the long polymeric chains. The author has developed a new method of the polymerization system called “vine-twining polymerization” for the formation of well-defined polysaccharide supramolecules, that is, amylose–polymer inclusion complexes. The method was achieved by phosphorylase-catalyzed enzymatic polymerization of α-D-glucose 1-phosphate (G-1-P) monomer from malooligosaccharide primer to produce amylose, in the presence of hydrophobic synthetic guest polymers. The image of this polymerization system is the similar as the way that the vines of a plant grow twining around a rod. By means of this method using designed guest polymers, the author has prepared hierarchically controlled amylosic supramolecular network materials, which formed hydrogels in aqueous media. For example, the author performed the preparation of supramolecular network hydrogels by the vine-twining polymerization using graft copolymers composed of hydrophobic graft guest polymers, such poly(γ-glutamic acid-graft-ε-caprolactone) (PGA-g-PCL). A supramolecular network hydrogel was obtained with the progress of the vine-twining polymerization, which showed a self-standing property. Macroscopic interfacial healing was achieved by the formation of inclusion complexes at interface between two hydrogel pieces through the enzymatic polymerization. A porous cryogel based on supramolecular network structure was obtained by lyophilization of a hydrogel. The XRD result of the lyophilized sample indicated the presence of inclusion complexes of amylose with the PCL graft-chains between intermolecular (PGA-g-PCL)s, which acted as supramolecular cross-linking points for the hydrogelation. Furthermore, ion gels were fabricated by soaking the hydrogels in an ionic liquid, 1-butyl-3-methylimidazolium chloride.