Sedimentation polymerization of an aqueous 2-hydroxyethyl acrylate solution with some crosslinkers was carried out using a simple sedimentation polymerization apparatus to give millimeter-size and very narrow size distributed poly(2-hydroxyethyl acrylate) (PHEA) gel beads. Also, heterogeneous acetylation of the resulting PHEA gel beads with acylating agents such as acetic anhydride, a mixture of acetic anhydride and pyridine, and chloroacetic anhydride was performed under various conditions. The selective esterification of PHEA gel beads proceeded smoothly in toluene from surface to give a novel core-shell type gel consisting of an unreacted core and acetylated shell, and finally afforded almost quantitatively acetylated PHEA gel. The unreacted core became small while maintaining a spherical shape during reaction. The reaction resembled to that of the corresponding cylindrical PHEA gel, and was strongly affected by the network structure of the obtained PHEA gel beads and the reactivity of acylating agents. (C) 2005 Published by Elsevier Ltd.