Emulsion electrospinning using natural and synthetic polymers, including two dissimilar materials is a promising technique for nanofibers fabrication in a core/shell configuration for tissue engineering, controlled or sustained drug delivery and dressing applications. In this study, we designed and fabricated core/shell nanofibers based on polycaprolactone (PCL) as core material and poly(vinyl alcohol) (PVA)‐gelatin (GEL) blend as shell materials (PCL/PVA‐GEL) to achieve high mechanical properties, good cell growth, and proliferation via emulsion electrospinning. The effect of water to acetic acid ratio in the solvent system (8:2, 7:3, 6:4, 5:5) and also type and concentration (3, 5, 7 w/v %) of surfactant on emulsion stability and nanofibers morphology were investigated. The emulsion containing 2% Tween80 and 1% Span60 as surfactants were selected by considering the stability of emulsion and uniform fiber morphology. In the tensile strength and elongation at break, 53 and 8% increase in the crosslinked wet state of the PCL/PVA‐GEL nanofibers compared with PVA‐GEL nanofibers were observed respectively. The cell culture results indicated that the PCL/PVA‐GEL nanofibers surface has presented suitable interaction with fibroblast cells and cells attached and proliferated well on the fabricated substrate within 24 and 48 hours and also would be a good candidate for biomedical applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48713.
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