Enhancing Crystallinity of Electrospun Polylactic Acid Fibers: Insights into Formation Mechanisms and Property Modulation–A Review

ABSTRACT Polylactic acid (PLA) electrospun fibers often lack sufficient crystallinity, which limits their mechanical strength, thermal stability, and functional performance. Tailoring a specific degree of crystallinity is therefore required for expanding the use of PLA fibers in various fields, where durability, degradation, and processability depend on controlled polymorphic phases. This review highlights recent studies on optimizing crystallinity by tuning electrospinning parameters to control fiber alignment and enhance molecular ordering. It also covers adding nucleating agents or fillers to lower crystallization barriers and using thermal or solvent annealing post‐treatments to stabilize phases. Various additives have been demonstrated to modify the crystallinity of PLA electrospun fiber mats, influencing the balance between β‐phase piezoelectricity, α′ (metastable) and α (stable) phases, and α′→α phase transition during solvent evaporation. Scalable hybrid techniques and green processing approaches are emphasized to address sustainability concerns, while advances in real‐time monitoring are highlighted as promising tools for achieving precise control over crystallization. This review synthesizes current knowledge to guide the design of PLA electrospun fibers with tailored crystallinity, balancing mechanical integrity, functional versatility, and environmental impact.