In this study silver nanoparticles were synthesized by microwave irradiation method using soluble starch as a green capping and reducing agent. The as-prepared soluble starch coated silver nanoparticles (S-Ag NPs) were incorporated in polyvinyl alcohol (PVA) matrix to fabricate nanofibers through electrospinning process. Two different types of crosslinking treatments were used to make the nanofiber mats insoluble in physiological environments. Experimental studies revealed that the choice of the crosslinking treatment led to affect the silver ion release. The nanofiber mats crosslinked with glutaraldehyde have superior silver ion release and stability in simulated body fluid (SBF). The released amounts of silver ions were lower than the toxic level of silver ions for HaCat keratinocytes and human epidermal keratinocytes. After proving antibacterial properties of the glutaraldehyde crosslinked S-Ag NPs loaded PVA nanofiber mats against E. coli and S. aureus it was thought that the nanofibrous mats fabricated in this study can be good candidates as antibacterial scaffolds for wound dressing applications.