Over the past two decades, biomass‐derived and biodegradable polylactide (PLA) has sparked tremendous attention as a sustainable alternative to traditional petroleum‐derived polymers for diverse applications. Unfortunately, the current applications of PLA have been mainly limited to biomedical and commodity fields, mostly because the poor heat resistance (resulting from low melting temperature) and hydrolysis stability make it hard to use as an engineering plastic. Stereocomplexation between enantiomeric poly(l‐lactide) (PLLA) and poly(d‐lactide) (PDLA) opens a new avenue toward PLA‐based engineering plastics with improved properties. The formation, crystal structure, properties, and potential applications of stereocomplex‐type PLA (SC‐PLA) are summarized by some research groups. However, since it is challenging to achieve full stereocomplexation from high‐molecular‐weight PLLA/PDLA blends and to avoid serious thermal degradation of the PLAs after complete melting, the advances and progress in the processing of SC‐PLA into useful products are quite rare in open publication. In this review, some important strategies for enhancing stereocomplex crystallization in practical processing operations are presented and recently developed processing technologies for SC‐PLA are highlighted, such as low‐temperature sintering. Furthermore, major challenges and future developments are briefly discussed. This review is expected to potentially open up new research activities in the processing of SC‐PLA.

Selective cross-linking of PLLA and PDLA chain couples in the amorphous phase allows for the formation of stereocomplex (sc) crystallites in the continuous melting and recrystallization process to be perfectly reversible.

Preparing super-tough and heat-resistant PLLA/elastomer blends by constructing stereocomplex crystallites at the interface to simultaneously tailor interface and matrix properties.