Abstract Summary: A novel type of glycerol‐derived, water‐soluble polycarbonate with pendant, primary hydroxyl groups was prepared from 2‐(2‐benzyloxyethoxy)trimethylene carbonate (BETC). Ring‐opening polymerization of BETC and 2,2‐dimethyltrimethylene carbonate (DTC) gave narrow distribution of homopolymers or random copolymers with high molecular weights. The protecting benzyl groups were removed by catalyzed hydrogenation at atmosphere H2 pressure to give hydroxyl polycarbonates without observable changes on the polymer backbone and molecular weight distribution. The hydrophilicity of the copolymers increases with the increase in the hydrophilic glycerol‐derived carbonate content. Synthesis of the glycerol‐derived polycarbonate. magnified image Synthesis of the glycerol‐derived polycarbonate.