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The one-step incorporation of ascorbyl palmitate (AP), a widely used derivative of vitamin C, into nanofibrous mats of poly(ε-caprolactone) (PCL) by electrospinning was demonstrated. The incorporation of AP was attested by IR spectroscopy; the AP content was determined by thermogravimetric analysis (TGA); and the surface composition of the mats: by X-ray photoelectron spectroscopy (XPS). The possibility for deposition of silver nanoparticles onto PCL/AP mats using the ability of AP to reduce silver ions was demonstrated. The silver content was determined by TGA, and the silver nanoparticles were observed by transmission electron microscopy (TEM). The nanoparticles were composed of elemental silver, as verified by XPS analyses. The UV–vis spectrophotometric analyses, study on quenching of the free 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals and microbiological tests against the pathogenic microorganism Staphylococcus aureus showed that AP preserved its stability and its antioxidant and antibacterial activity when incorporated in the nanofibrous mats.