Cholesterol-linked polysaccharides were prepared by reacting monocholesterylsuccinate (ChMS) with cellulose acetate [AC; degree of substitution (DS) 1.00, 1.80, and 2.33], ethyl cellulose (EC; DS 2.46), starch, and hydroxyethyl starch (HES; molar substitution, 0.05-0.07). The degree of ChMS substitution ranged from 0.27 to 1.29. The polymers were characterized by IR, NMR, DSC, and hot-stage coupled polarizing microscopy. Polymers with a higher DS of ChMS showed a thermotropic liquid crystalline behavior.