Chitosan is a polysaccharide with promising industrial and biomedical applications, owing to its intrinsic electrostatic interactions with negatively charged cells, providing outstanding antimicrobial activity. For use in fiber structures, several parameters must be controlled by incorporating additives to achieve desirable porosity and surface area for wound-dressing applications, such as polymer templates, metal nanoparticles, and functional groups as crosslinking agents. These compounds provide adequate control over porosity and absorptivity, which can be combined to achieve desirable conditions for gas exchange and microbial capture in the resulting electrospun fibers. In this review, the potential and bottlenecks for the scalability and industrial application of chitosan-based biomedical fibrillar prototypes are discussed, underscoring the relevance of toxicological assays in elucidating their potential across several areas, including food packaging, smart dressings, controlled-release systems, and antimicrobial coatings.