Poly(ethylene oxide)-block-poly(methacryl-d-glucopyranoside) (PEO-GP) and poly(methacryl-d-glucopyranoside) (H-GP) glycopolymers were synthesized by deacetylation of acetylated polymers which were synthesized via atom transfer radical polymerization. The synthesized glycopolymers were characterized using 1H NMR, 13C NMR and Fourier transform infrared (FTIR) spectroscopies, gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The deacetylated polymers exhibited onset decomposition temperatures about 60 °C lower compared to the polymers having acetyl pendants. The glass transition temperature (Tg) of the acetylated homopolymer was 133 °C and that of the PEO-based block copolymer was 124 °C. The deacetylated polymers H-GP and PEO-GP exhibited Tg values of about −30 °C. Biocompatibility of the H-GP and PEO-GP glycopolymers was obtained by studying osteoblast cell adhesion, viability and proliferation in vitro. The cell viability showed an increase with increasing concentration of H-GP from 0.1 to 1 µmol L−1 and then decreased with further increase in its concentration (10–1000 µmol L−1). PEO-GP did not show a significant variation in cell viability on variation of its concentration from 0.1 to 1000 µmol L−1. The significant improvement in biocompatibility with osteoblast cells in the presence of PEO-GP was considered as due to the covalently bonded PEO segment of the methacrylate glycopolymer block.