In this article, we report the facile one-pot synthesis of poly(decamethylene succinate) (PDS) with multiple hydroxyl groups by direct polycondensation with malic acid (MA) as the functional monomer and dysprosium triflate as the chemoselective catalyst at 80 degrees C. The secondary hydroxyl groups of malic units were inactive during the polycondensation process. The density of hydroxyl groups of the copolymer could be well-controlled by the molar ratio of succinic acid and MA in the feed. These hydroxylated PDSs were grafted by poly(ethylene glycol) (PEG) through a simple esterification reaction; this resulted in amphiphilic PDS-g-PEG copolymers, which could undergo micellization in aqueous media to form nanosized aggregates with diverse morphologies and diameters. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013.