The present study demonstrates a strategy for preparing porous composite fibrous materials with superior biocompatibility and antibacterial performance. The findings reveal that the incorporation of PEG into the spinning solutions significantly influences the fiber diameters, morphology, and porous area fraction. The addition of a hydrophilic homopolymer, PEG, into the Ch/PLA spinning solution enhances the hydrophilicity of the resulting materials. The hybrid fibrous materials, comprising Ch modified with PLA and PEG as a co-solvent, along with post-treatment to improve water stability, exhibit a slower rate of degradation (stable, moderate weight loss over 16 weeks) and reduced hydrophobicity (lower contact angle, reaching 21.95 ± 2.17°), rendering them promising for biomedical applications. The antibacterial activity of the membranes is evaluated against Staphylococcus aureus and Escherichia coli, with PEG-containing samples showing a twofold increase in bacterial reduction rate. In vitro cell culture studies demonstrated that PEG-containing materials promote uniform cell attachment, comparable to PEG-free nanofibers. The comprehensive evaluation of these novel materials, which exhibit improved physical, chemical, and biological properties, highlights their potential for biomedical applications in tissue engineering and regenerative medicine
