Infections related to biomedical devices and materials remain a critical healthcare concern, leading to considerable morbidity and disease burden. To combat this issue, the development of fibers with inherent antibacterial properties has garnered significant interest. These fibers offer a large surface area, making them ideal candidates for effective treatment with antibacterial agents. In this study, we present a straightforward procedure for applying silver nanoparticles (AgNPs) to hydrophobic polylactic acid (PLA) fibers that have been surface-modified using sodium hydroxide (NaOH). The method involved electrospinning to create a high-thickness web of PLA fibers, followed by gradual surface modification with NaOH at two different concentrations (0.5 M and 1 M). To confer antibacterial properties to the modified surface samples, we applied silver nanoparticles (AgNPs) at a concentration of 25 mM. In contrast to regular PLA fibers, the surfaces of hydrolyzed PLA (PLA-H) fibers, AgNPs-treated PLA (PLA-A), and hydrolyzed-AgNPs coated PLA (PLA-H-A) fibers exhibited a non-uniform and highly porous structure. EDX analysis provided crucial information about the presence and integration of Ag nanoparticles into the PLA fibers. The PLA-H-A sample exhibited the highest hydrophilicity, with a contact angle of 65.7°. Additionally, the results from differential scanning calorimetry indicated an increase in PLA-H-A's glass transition temperature. Notably, in the Gram-positive Escherichia coli (E. coli) and Gram-negative Staphylococcus aureus (S. aureus) tests, the PLA-H-A samples demonstrated highly effective antibacterial properties, effectively preventing bacterial growth.