Non‐Covalent Structural Reinforcement of Electrospun Polyvinylpyrrolidone ( PVP )/Polyethylene Oxide ( PEO ) Fibers Through Combined Crosslinking Treatments

Electrospun polymeric fibers provide versatile platforms for advanced material design; however, their stability and performance often depend on effective crosslinking strategies. In this study, electrospun fibers were produced from blends of polyvinylpyrrolidone (PVP, amorphous) and polyethylene oxide (PEO, semicrystalline) at different ratios (25:75, 50:50, and 75:25). To improve their physicochemical, morphological, and dynamic‐mechanical properties, the electrospun fibers were subjected to combinations of crosslinking strategies, including glutaraldehyde (GA) addition, freeze–thaw cycling (FT), and UV irradiation (UV). The combination of crosslinking methods enhanced the dynamic‐mechanical properties without compromising fiber integrity. The addition of GA to the fibers increased the fiber diameter and restricted segmental mobility at the molecular level without inducing the formation of covalent bonds. When GA is combined with FT or UV treatments, chain alignment is promoted, leading to a crystallinity increase of 75%–100% depending on PEO content, leading to improved structural order. In PEO‐rich blends, this effect was mediated by interactions with PEO hydroxyl groups and potential hydrogen bonding with PVP carbonyls, resulting in superior mechanical strength, thermal stability, and cooperative chain relaxation. In PVP‐rich blends, hydrogen‐bonded interactions enhanced stiffness, rigidity, and stability. Among all treatments, GA–UV crosslinking produced the highest crystallinity and mechanical stiffness, confirming its effectiveness for stabilizing electrospun PVP/PEO fibers. These findings highlight the pivotal role of semicrystalline PEO in governing the structural and dynamic mechanical behavior of electrospun fiber systems, providing fundamental insights for designing polymer blends with tailored properties.