Poly(ether sulfone) hollow fibers modified with various polysaccharides were used to immobilize Cibacron Blue 3GA for affinity adsorption. Characterization of modified hollow fibers with respect to their activation using ethylene glycol diglycidyl ether, conjugation with polysaccharides, and immobilization with Cibacron Blue 3GA indicates that the surface modification was successfully achieved. This work also studied the adsorption behavior of lysozyme onto immobilized Cibacron Blue 3GA using the polysaccharide-modified fibers as solid supports. The optimal adsorption capacity was observed from the hollow fibers conjugated with hydroxyethyl cellulose or dextran derivative and with high density of immobilized Cibacron Blue 3GA. Moreover, the effect of temperature on lysozyme adsorption was investigated. The results show that the lysozyme-ligand binding on the polysaccharide-modified hollow fibers tends to be endothermic.