Stereocomplex (sc) crystallization of enantiopure polymers is a special crystallization manner of macromolecules. Due to the unique structure, the stereocomplexed materials have many merits such as the higher melting point, higher heat resistance, high mechanical strength and modulus, better hydrolytic resistance, and also better physical performances in the biomedical applications such as drug delivery and tissue engineering. One of the most studied examples of polymer stereocomplexation is poly(lactic acid) (PLA). Poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA) are a representative enantiomeric pair that can crystallize in stereocomplex in their polymeric racemic blends and stereoblock copolymers. The stereocomplexed PLA has an enhanced Tm of 230 C, which is about 50 C higher than their homocrystalline parent polymers. However, the sc crystallization just takes place in the PLLA/PDLA enantiomeric blends with the low molecular weights. For the high-molecular-weight PLLA/PDLA blends, only the homocrystallites with lower Tm are formed. In this work, we have found several methods including the stereoblock copolymerization, miscible blending, chain terminal modification, macromolecular topological control, and heterogeneous nucleation to increase the sc crystallization and diminish the homocrystallization of high-molecular-weight PLAs. The competing crystallization kinetics, polymorphic crystalline structure, and crystalline phase transition in these PLLA/PDLA stereoblock copolymer and blends were studied. The mechanism for the enhanced sc crystallization in these systems were discussed. Furthermore, the heat-resistant materials of PLAs were prepared through promoting the sc crystallization. References: Pan, et al. Macromolecules 2015, 48, 7872; J. J. Phys. Chem. B 2015, 119, 14270; J. Phys. Chem. B 2015, 119, 12689; J. Phys. Chem. B 2015, 119, 6462; Polymer 2015, 63, 144; Macromolecules 2014,47, 8126.