AbstractA new disaccharide monomer, 6(‐methacryloxyloxy)hexyl β‐D‐cellobioside (CHMA,7h), was prepared through a five‐step procedure (starting from cellobiose), in which the glycosylation and esterification reactions have been optimized. Kinetics of radical homopolymerization in dimethyl sulfoxide solution were studied through1H NMR, allowing the determination of the parameterkp/kt1/2. Copolymerizations with styrene (S) were also investigated, giving the reactivity ratiosrS= 0,64 andrM= 0,08. Characterization of the various (co)polymers in terms of composition, microstructure and molecular weight was carried out using1H and13C NMR spectroscopy and gel‐permeation chromatography in tetrahydrofuran, respectively. A preferential syndiotactic configuration was clearly evidenced in the h