Poly(delta-valerolactone) [poly(deltaVL)] of high molecular weight (similar to40 000) and low polydispersity index (similar to1.05) was prepared by activated monomer cationic ring-opening polymerization of delta-VL initiated by the alcohol/HCl.Et2O system. A series of functional alcohols, e.g., 9-anthracenemethanol, 2-hydroxyethyl acrylate, 3-buten-1-ol, 2-bromoethanol, and 5-norbornene-2-metbanol, were successfully used to prepare asymmetric telechelic poly(deltaVL), i.e., chains end-capped by the functional group of the alcohol in a-position and by an w-hydroxyl group. Ring-opening polymerization of delta-VL in the presence of alpha-methoxy-w-hydroxylpoly(ethylene oxide) and poly(ethylene glycol) led to amphiphilic di- and triblock copolymers, respectively. The polydispersity index of all these (co)polymers was low (similar to1.10).