Glycol chitosan (GC) and methyl glycol chitosan (MGC) were separately reacted with poly(potassium vinyl sulfate) (PVSK) in the presence of iron(III) hydroxide sulfate (IHS) to form water-insoluble macromolecular complexes (MC's). The chemical compositions and properties of MC's obtained were compared with each other. The solubility of MC in the MGC-IHS-PVSK system was lower than that in the GC-IHS-PVSK system, and it was suggested that MGC contributes to the properties of MC.