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A green electrospinning was used for the fabrication of PVA/Dex (dextran sulfate) nanofibers as a carrier for drug delivery. Core-shell nanofibers were fabricated by emulsion electrospinning from PVA/Dex loaded with ciprofloxacin (Cipro) as a model drug. The ratio of the PVA/Dex mixture was optimized and nanofibers were stabilized against disintegration in water by thermal treatment at 120 °C. The morphology of the prepared nanofibers was observed by scanning electron microscopy (SEM) and the core-shell structure of the nanofibers was confirmed by transmission electron microscopy (TEM). Drug entrapment was confirmed by Fourier-transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The interaction between PVA and Dex was affirmed by differential scanning calorimetry (DSC). In vitro drug release was monitored by UV-vis spectrophotometer and its associated mechanism was studied using diverse kinetic models. The release study demonstrated that the core-shell nanofibers can sustain the Cipro release compared with the blending electrospinning nanofibers. Moreover, the drug release mechanism is controlled by the Dex content of the polymer blends and can occur by diffusion within the delivery system. It is anticipated that Cipro@PVA/Dex nanofibers are promising eco-friendly drug delivery system which can be prepared by a green method., (Copyright © 2018 Elsevier B.V. All rights reserved.)