A new class of rod-coil block copolymers is synthesized by chemoenzymatic polymerization. In the first step, maltoheptaose, which acts as a primer for the synthesis of amylose, is attached to poly(2-vinyl pyridine) (P2VP). The enzymatic polymerization of maltoheptaose is carried out by phosphorylase to obtain amylose-b-P2VP block copolymers. The block copolymer is characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and wide-angle X-ray scattering techniques. The designed molecules combine the inclusion complexation ability of amylose with the supramolecular complexation ability of P2VP and therefore this kind of rod-coil block copolymers can be used to generate well-organized novel self-assembled structures.