Compared with linear diblock or triblock poly(ethylene glycol)-block-poly(L-lactic acid) copolymer (PEG-b-PLLA), star-shaped PEG-b-PLLA (sPEG-b-PLLA) copolymers exhibit smaller hydrodynamic radius and lower viscosity and are expected to display peculiar morphologies, thermal properties, and degradation profiles. Compared with the synthesis routine of PEG-b-PLLA form lactide and PEG, the traditional synthesis routine from LA and PEG were suffered by the low reaction efficiency, low purity, lower molecular weight, and wide molecular weight distribution. In this article, multiarm sPEG-b-PLLA copolymer was prepared from multiarm sPEG and L-lactic acid (LLA using an improved method of melt polycondensation, in which two types of sPEG, that is, sPEG1 (four arm, Mn = 4300) and sPEG2 (three arm, Mn = 3200) were chosen as the core. It was found the molecular weight of sPEG-b-PLLA could be strongly affected by the purity of LLA and sPEGs, and the purification technology of vacuum dewater and vacuum distillation could help to remove most of the impurities in commercial available LLA. The polymers, including sPEG and sPEG-b-PLLA with varied core (sPEG1 and sPEG2) and LLA/sPEG feeding ratios, were characterized and confirmed by 1H-NMR and 13C-NMR spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography, which showed that the terminal hydroxyl group in each arm of sPEGs had reacted with LLA to form sPEG-b-PLLA copolymers with fairly narrow molecular weight distribution. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011