Polyvinyl alcohol (PVA) nanofibers produced by electrospinning are attractive for biomedical and antimicrobial applications due to their biocompatibility and ease of processing in aqueous systems. However, their inherent water solubility and lack of intrinsic antimicrobial activity limit practical use. This study reports the fabrication of water-stable electrospun PVA nanofibers via glutaraldehyde (GA) vapor crosslinking, followed by in situ incorporation of silver nanoparticles (Ag NPs) to enhance antimicrobial functionality. In this study a 10 wt % PVA solution was electrospun under controlled parameters (10 kV, 0.27 mL/h, 7 cm tip-to-collector distance, and 70 % relative humidity). Crosslinking was performed using GA/HCl vapor treatment for 24 h. Ag NPs were deposited onto crosslinked PVA nanofibers (cPVA) through chemical reduction using AgNO₃ as a precursor and NaBH₄ as a reductant agent. Morphological, structural, and chemical characterization was carried out using SEM, EDX, FTIR, and Raman spectroscopy. Nanoparticle size distribution was analyzed with ImageJ software. Electrospun PVA nanofibers exhibited an average diameter of approximately 140 nm, which increased to ~170 nm after crosslinking, confirming successful structural modification. FTIR and Raman spectra verified acetal bridge formation between PVA and GA. Ag NPs with size distributions between 12 and 20 nm were homogeneously deposited using the chemical reduction method, showing reduced agglomeration compared to Tollens-based synthesis. The modified nanofibers demonstrated structural stability in water and surface chemical interactions between silver and acetal groups. In this manner, GA vapor crosslinking effectively rendered PVA nanofibers water-insoluble while preserving morphology. Controlled in situ reduction enabled uniform Ag NP incorporation, producing nanofibrous composites with potential for antimicrobial biomedical applications.