Six styrene derivatives meta-substituted with acetal-protected glucofuranoses (1) and (2), galactopyranose (3), fructopyranose (4), and sorbofuranose (5) and para-substituted with acetal-protected glucofuranose (6) were synthesized by the Williamson reactions of m- or p-(chloromethyl)styrene with the corresponding protected monosaccharides in DMF and were anionically polymerized. The anionic polymerizations were carried out with s-BuLi in THF at -78 degrees C for 30 min. Among the monomers, 1-5, were found to undergo anionic Living polymerization to afford quantitatively the polymers of predictable molecular weights and narrow molecular weight distributions (M-w/M-n < 1.13). Novel well-defined block copolymers, polystyrene-block-poly(1) starting either from living polystyrene or the living polymer of 1, were successfully synthesized. By contrast, no appreciable polymerization of 6 occurred under identical conditions.