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Abstract Nanofibers made by blending natural and synthetic biopolymers have shown promise for better mechanical stability, ECM morphology mimicry, and cellular interaction of such materials. With the evolution of production methods of nanofibers, alternating field electrospinning (a.k.a. alternating current (AC) electrospinning) demonstrates a strong potential for scalable and sustainable fabrication of nanofibrous materials. This study focuses on AC‐electrospinning of poorly miscible blends of gelatin from cold water fish skin (FGEL) and polycaprolactone (PCL) in a range of FGEL/PCL mass ratios from 0.9:0.1 to 0.4:0.6 in acetic acid single‐solvent system. The nanofiber productivity rates of 7.8–19.0 g/h were obtained using a single 25 mm diameter dish‐like spinneret, depending on the precursor composition. The resulting nanofibrous meshes had 94%–96% porosity and revealed the nanofibers with 200–750 nm diameters and smooth surface morphology. The results of FTIR, XRD, and water contact angle analyses have shown the effect of FGEL/PCL mass ratio on the changes in the material wettability, PCL crystallinity and orientation of PCL crystalline regions, and secondary structure of FGEL in as‐spun and thermally crosslinked materials. Preliminary in vitro tests with 3 T3 mouse fibroblasts confirmed favorable and tunable cell attachment, proliferation, and spreading on all tested FGEL/PCL nanofibrous meshes.