Poly(L-lactic acid) (PLLA) of high molecular weight was prepared by a chain-extending reaction in a microcompounder. Phosphites were used as chain extenders to increase the molecular weight of the PLLA prepolymer, which was prepared by the bulk polycondensation of l-lactic acid. The effects of the amount of phosphite, the temperature, and the screw speed on the torque of the PLLA melt were studied. Under the optimal conditions, the molecular weight of PLLA increased from 62,100 to 126,000 g/mol. The chemical structure and crystallinity of PLLA were characterized by Fourier transform infrared spectroscopy, 1 H-NMR and 13 C-NMR, differential scanning calorimetry, and X-ray diffraction. The mechanical properties of PLLA were measured. The results indicate that triphenyl phosphite (TPPi) was an effective chain extender for PLLA. The role of the TPPi in chain extending is suggested to be an esterification-promotion agent.