Galactose moieties were covalently coupled with alginate through ethylenediamine as the spacer for enhancing the interaction of hepatocytes with alginate. Adhesion of hepatocytes onto the galactosylated alginate (GA)-coated polystyrene (PS) surface showed an 18-fold increase as compared with that of the alginate-coated surface and it increased with an increase in the concentration of GA. The morphologies of attached hepatocytes were observed to spread out at the 0.15 wt% GA-coated PS surface while round cells were observed at the 0.5 wt% GA-coated PS surface. Inhibition of hepatocytes attachment onto the galactose-carrying PS-coated surface occurred with the addition of the GA into the hepatocyte suspension, indicating the binding of GA with hepatocytes via the patch of asialoglycoprotein receptors. Primary hepatocytes were entrapped in the GA/Ca2+ capsules (GAC). Higher cell viability and more spheroid formation of hepatocytes were obtained in the GAC than in the alginate/Ca2+ capsules (AC). Moreover, liver functions of the hepatocytes such as albumin secretion and urea synthesis in the GAC were improved in comparison with those in the AC.