Core-shell-structured polyvinyl alcohol (PVA)-poly (lactic acid) (PLA) nanofibers combining the hydrophilic trait of PVA and the biocompatibility of PLA were produced using coaxial electrospinning. This allowed the incorporation of AgNO3 in the PVA core of the distinct fibers as shown through transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). Scanning electron microscopy (SEM) showed relatively uniform and bead-free fibers with smooth surfaces. Ag-containing fibers show significantly decreased diameters compared with Ag-free samples as a result of the increased conductivity of the spinning solutions with increasing amounts of AgNO3. In a postsynthetic treatment, the AgNO3 was reduced forming silver nanoparticles (Ag NPs). Ag NPs of 45 to 90 nm size were located in the PVA core but also on the surface of the core-shell fibers and as individual, agglomerated, and polymer-coated particles of 100-200 nm. Powder X-ray diffraction (PXRD), energy dispersive X-ray spectroscopy (EDX), and UV-vis absorption spectroscopy confirmed the increasing amounts of Ag in the core-shell fibers when using increasing amounts of AgNO3 in the spinning solutions. The antibacterial activity of the nanofiber mats against two prokaryotes Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) increased with increasing amounts of Ag, as expected and produces inhibition zones of 1 to 2 mm.