Lithium chloride was found to be an effective and biocompatible catalyst for the ring-opening polymerization of lactide in the presence of hydroxyl-containing compounds. Ethylene glycol (EG) and methyl alpha-D-glucopyranoside (MGlc) were used as multifunctional initiators. The polymerization was carried out as 128 degrees C in bulk with 1% (w/w) of LiCl. Polylactide (PLA) of different molecular weights was obtained with varied molar ratios of monomer/initiator ([M](0)/[I](0)). The LiCl-catalyzed ring-opening polymerization was applied to the synthesis of a number of amphiphilic PLA copolymer when poly(ethylene glycol) (PEG), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose (HEC), and hydroxypropyl cellulose (HPC) were used as macroinitiators.