Saccharification of a glass surface has been performed using two grafting methods: grafting-from and grafting-onto, using a sugar-based cyclic sulfite as monomer. Central to the technique is a cationic ring-opening polymerization of the cyclic sulfite, which proceeds via the clean elimination of SO2 to yield 1,2-glucopyranan-grafted materials. The obtained glass surfaces exhibit different thermo-responsive behaviors, which could be attributed to features of each grafting method.