In order to enhance the content of stereocomplex crystals (SC) in poly L-lactic acid (PLLA)/poly D-lactic acid (PDLA) symmetric blend, thereby improving the defects of low crystallinity and poor heat resistance of polylactic acid (PLA)-based materials, the samples with different entanglement degrees were prepared by freezing extration method. The critical overlap concentration of the blend system was quantitatively obtained using an Ubbelohde viscometer. Based on this concentration, samples with a series of concentration gradient were prepared to control the different degrees of molecular chain entanglement inside. The results indicated that the chain disentanglement could greatly increase the content of SC in the blend, whether in the precipitation crystallization or the melt crystallization process. Especially after the isothermal crystallization for 30min at 130oC, the L/D-0.1 sample with the highest degree of disentanglement almost only formed SC, accounting for 95.2% of the total crystallinity. Samples with lower entanglement degree had more crystal nuclei and faster growth rate of formed spherulites. For completely entangled sample L/D-50, the crystal nucleus of homo-crystalls (HC) could be considered as SC. Besides, the Vicat softening temperature (VST) of L/D-0.1 sample increased from 79.9oC of L/D-50 sample to 103.8oC with an obvious increase of 24.9oC. All these results provide new ideas for improving the performance of PLA-based materials and show promising development prospects of green and sustainable polymers.