Polyhydroxyurethane bearing silicone backbone was prepared by polyaddition of silicone diamines with a bifunctional five-membered cyclic carbonate prepared from the corresponding diepoxide and CO2. Polymerization in propylene glycol methyl ether acetate proceeded smoothly, and polymers could be obtained in high yields under appropriate conditions. The introduced silicone moieties improved the hydrophobicity and lowered the glass transition temperature keeping thermal stability. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1113-1118