Poly(vinyl pyrrolidone) (PVP) and nanosilver are promising candidates for biomedical applications because of their biocompatibility and antibacterial efficacy, respectively. In this research, three kinds of nanosilver particles (NSPs) were prepared using the seed mediate growth method and added to electrospinning solutions. PVP/NSPs composites were prepared by electrospinning of 10 wt% PVP solutions that contained NSPs in ethanol. The electrospinability of PVP/NSPs nanowebs in ethanol was investigated according to three different concentrations of NSPs. The Electrospun PVP/NSPs nanocomposites were photocross-linked to improve their water stability. The antibacterial efficacy of the PVP/NSPs nanocomposites was assessed against three types of bacteria; Staphylococcus aureus, Klebsiella pneumoniae and Escherichia coli. The photocross-linked PVP/NSPs nanocomposites had high water stability and significant antibacterial efficacy against all three types of bacteria. Therefore, these composites could be applied as antimicrobial materials.