We examine a one-step process to fabricate metal nanoparticle (NP)-alginate polymer nanofiber (NF) composites via electrospinning for biomedical applications. Alginate, a natural biopolymer extracted from seaweeds used as an additive in pharmaceutical and food formulations, is widely known to promote optimal environment for wound healing. However, we have found that alginate in aqueous solution cannot be electrospun by itself in all concentrations up to saturation. We report the successful generation of electrospun NFs based on alginates with the addition of minute amount of surfactants. The effect of surfactant addition on solution properties as it relates to electrospinning is determined using rheological and microscopy techniques. Furthermore, the novel use of the electrospinning polymer blend acting as both the reducing and protecting agent for the NPs is also investigated. A model system that involves alginate and poly (ethylene oxide) (PEO) blends and a metal salt to generate NF composites is presented. The nanofiber composites have potential as wound dressing with antimicrobial properties. We demonstrate by UV/Vis spectrophotometry that PEO and alginate transform Ag ions to Ag NPs without the addition of any reducing agent and stabilizer. Interesting nanostructures that are well-dispersed and crystalline at or near the NF surface are observed from TEM, XRD and XPS analyses. The antimicrobial property of the NF mats against various model microbes is evaluated.