High molecular weight(Mw) poly(L-lactic acid)s(PLLAs) were synthesized using multifunctional epoxy compound(Joncryl-ADR4370) as chain extender. The products were characterized by gel permeation chromatography(GPC) and spectroscopy(1HNMR and FTIR). The results indicated that the Mw of PLLA increased with the increasing of the ratio of epoxy compound and the extending of reaction time. The highest Mw of PLLA reached 360 000 g/mol when the ratio of epoxy compound was 1.5 wt%. However, the reactants turned to cross-linking when the ratio of epoxy compound was over 1.5 wt%. Differential scanning calorimetry(DSC) measurements demonstrated that the glass transition(Tg) and melting temperatures(Tm) of products increased slightly as the increase of the molecular weight. Analysis of the hydrolytic degradation in vitro showed that the branched PLLA possessed the quicker degradability than that of the linear PLLA.