The experimental UV-vis spectrum of the glycogen-iodine (GI) complex shows certain features remarkably similar to that of the amylopectin-iodine (API) complex [J. Polymer. Chem. 32, 2257 (1994)], suggesting a strong similarity between the API and the GI structures. As in the API complex, a nearly linear polyiodine unit, I-4, at an interiodine distance of around 3 Angstrom is expected to exist within the helix of 11 anhydroglucose units (AGUs). There are several other spectral features that suggest the presence of another similar but more loosely bound iodine species with a longer interiodine distance of 3.1 Angstrom. These findings suggest the involvement of two different types of glycogen chains in binding iodine molecules.