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°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. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013.