Ring-opening polymerization (ROP) of epsilon-caprolactone (CL) using salicylic acid (SAA) as the organocatalyst and benzyl alcohol as the initiator in bulk at 80 degrees C successfully proceeded to give a narrowly distributed poly(epsilon-caprolactone) (PCL). In addition, 2-hydroxyethyl methacrylate, propargyl alcohol, 6-azido-1-hexanol, and methoxy poly(ethylene glycol) were also used as functional initiators. The H-1 NMR, SEC, and MALDI-TOF MS measurements of the PCL clearly indicate the presence of the initiator residue at the chain end, implying that the SAA-catalyzed ROP of CL was through the activated monomer mechanism. The kinetic experiments confirmed the controlled/living nature of the SAA-catalyzed ROP of CL. Furthermore, the block copolymerization of CL and -valerolactone successfully proceeded to give poly(epsilon-caprolactone)-block-poly(-valerolactone). (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1185-1192