Amylose forms supramolecular inclusion complexes with polymeric guests in the phosphorylase-catalyzed enzymatic polymerization field, so-called "vine-twining polymerization". However, such inclusion complexes have not exhibited specific properties and processability as functional supramolecular materials. In this study, we found that amylosic inclusion complexes, which were obtained by vine-twining polymerization using a designed guest polymer, that is, an amphiphilic triblock copolymer poly(2-methyl-2-oxazoline-block-tetrahydrofuran-block-2-methyl-2-oxazoline), exhibited gel and film formation properties. The characterization results of the products suggested that enzymatically elongated amylose chains complexed with the polytetrahydrofuran block in the triblock copolymer. Accordingly, the outer poly(2-methyl-2-oxazoline) blocks constructed hydrophilic spaces among the inclusion complex segments. Furthermore, the presence of such outer blocks affected the lower regularity of crystalline alignment among the inclusion complex segments in the products. Such higher-order structures probably induced the formation of supramolecular soft materials, such as gels and films.