Amphiphilic, biodegradable block glycopolymers based oil poly(epsilon-caprolactone) (PCL) with various pendent saccharides were synthesized by combination of ring-opening polymerization (ROP) and "click" chemistry. PCL macroinitiators obtained by ROP of epsilon-caprolactone were used to initiate the ROP of 2-bromo-epsilon-caprolactone (BrCL) to get diblock copolymers, PCL-b-PBrCL. Reaction of the block copolymers with sodium azide converted the bromine groups in the PBrCL block to azide groups. In the final step, click chemistry of alkynyl saccharides with the pendent azide groups of PCL-b-PBrCL led to the formation of the amphiphilic block glycopolymers. These copolymers were characterized by H-1 NMR spectroscopy and gel permeation chromatography. The self-assembly behavior of the amphiphilic block copolymers was investigated using transmission electron microscopy and atomic force microscope, spherical aggregates with saccharide groups on the surface were observed, and the aggregates could bind reversibly with Concanavalin A. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3583-3594, 2009