Role of cross-linking in improving the spinnability of biopolymers for production of electrospun fibers/nanofibers

Continuous electrospinning (ES) of high-quality natural polymers is essentially dictated by their natural chain entanglement and viscoelastic behavior. By adjusting polymer chain interactions and promoting solution stability, cross-linking (C_link) offers an adaptable route of widening the ES window and attaining fiber morphologies with more uniformity, quality, and consistency. Here, in this review, a structured summary of the principles/techniques of physico-chemical and dynamic C_link methodologies for biopolymers (e.g., alginate, chitosan, gelatin, etc.), is highlighted. Mechanistic influences on how C_link fine-tunes spinnability, jet stability, and fiber morphology are discussed, alongside practical guidance for solution preparation, ES protocols, and polymer selection. Recent progress connecting C_link circumstances to fiber quality/performance are illustrated, with architecture-feature relationships crucial for application-oriented design. The review further outlines novel applications across biomedical scaffolds, functional packaging, and environmental approaches, addressing current challenges and future opportunities. By pairing translational strategies with mechanistic insights, this work offers a robust framework for advancing the electro-spinnability of biopolymers via C_link control.