Summary: The stereoselective polymerization of partial rac‐lactide was attempted by using crystallization during polymerization. Polymerizations were carried out with trifluoromethanesulfonic acid in a mixed solvent of toluene and octane. The molar content of L ‐lactate in the feed was 95%. Polymerization proceeded with the elimination of D ‐lactate by means of crystallization. Poly(L ‐lactic acid) (PLLA) crystals were first precipitated and then plate‐like poly(lactic acid) (PLA) crystals were finally obtained, of which the composition of L ‐lactate was 97.6% and the was 1.68 × 104.