Transparent electrodes based on silver nanofiber networks were synthesized via electrospinning and ultraviolet (UV) treatment. Silver trifluoroacetate (STA), which served as the metallic precursor, was added to a poly(methyl methacrylate) (PMMA) solution. Transparent electrodes were then fabricated by electrospinning this solution. The as-spun PMMA/STA nanofibers with an average fiber diameter of 637 nm were exposed to UV irradiation under ambient conditions, which triggered the photodecomposition of PMMA and the formation of silver nanoparticles (Ag NPs) from the photoreduction of the STA precursor. These photoinduced reactions progressively accumulated Ag NPs in the centers of the nanofibers, forming one-dimensional silver nanostructures with connected conductive domains. Material characterization was carefully conducted with respect to the morphologies, compositions, and decomposition/synthetic mechanisms of these electrospun nanofibers. The optical and electrical performances were also investigated as a function of the UV dosage. The optimized silver nanofiber network demonstrated an optical transparency of 83% at a wavelength of 550 nm and a sheet resistance as low as 500 Omega sq(-1).