In this study, we found that amylose-poly(glycolic acid-co-e-caprolactone) (P(GA-co-CL)) inclusion complexes were formed when phosphorylase-catalyzed enzymatic polymerization was performed in the presence of biodegradable P(GA-co-CL)s according to a vine-twining polymerization process. The X-ray diffraction patterns of the products showed the typical diffraction peaks due to inclusion complexes composed of amylose and guest compounds. In addition, the 1 H NMR spectra of the products showed the signals due to amylose and P(GA-co-CL), in spite of washing with good solvents for P(GA-co-CL), such as acetone and chloroform. These results suggested that the products were inclusion complexes composed of amylose and P(GA-co-CL). The compositional ratio of GA unit to CL unit in P(GA-co-CL)s did not affect the inclusion behavior of amylose. On the other hand, the results in the vine-twining polymerization using amorphous P(GA-co-CL)s and a crystalline poly(glycolic acid-block-ecaprolactone) (P(GA-b-CL)) as guest polymers indicated that the crystallinity of the guest copolymers strongly affected the formation of inclusion complexes with amylose. In addition, we found that lipase-catalyzed hydrolysis of P(GA-co-CL) in the inclusion complex was partly inhibited, probably because amylose, which surrounded P(GA-co-CL), prevented the approach of lipase.