The polymorphous crystallization and multiple melting behavior of poly(L-lactic acid) (PLLA) with an optical purity of 92 % were investigated after isothermally crystallized from the melt state by wide-angle X-ray diffraction and differential scanning calorimetry. Owing to the low optical purity, it was found that the disordered (a 0 ) and ordered (a) crystalline phases of PLLA were formed in the samples crystallized at lower (\95°C) and higher (C95°C) temperatures, respectively. The melting behavior of PLLA is different in three regions of crystallization temperature (T c ) divided into Region I (T c \ 95°C), Region II (95°C B T c \ 120°C), and Region III (T c C 120°C). In Region I, an exothermic peak was observed between the low-temperature and high-temperature endothermic peaks, which results from the solid-solid phase transition of a 0 -form crystal to a one. In Region II, the double-melting peaks can be mainly ascribed to the melting-recrystallization-remelting of less stable a crystals. In Region III, the single endotherm shows that the a crystals formed at higher temperatures are stable enough and melt directly without the recrystallization process during heating.