A new trithiocarbonate 1 bearing two hydroxyl moieties was synthesized and employed as a RAFT agent for radical polymerization of vinyl monomers. 1 mediated RAFT polymerizations of styrene and ethyl acrylate to give the corresponding polymers with predictable molecular weights and narrow molecular weight distributions. Structural analyses of the polymers with NMR and MALDI-TOF mass techniques revealed that they were telechelic ones, of which both chain ends were endowed with hydroxyl groups inherited from trithiocarbonate 1. Usefulness of these telechelic polymers as polymeric diol-type building blocks was demonstrated in their polyaddition with diisocyanates, which gave the corresponding polyurethanes. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013