Electrospinning with consequent thermal treatment consists in a carbon fiber production method that spins a polymer solution to create fibers with diameters around a few hundred nanome-ters. The thermal treatments are used for the cyclization and then carbonization of the material at 1700◦C for one hour. The unique structure of micro-and nano-carbon fibers makes them a promis-ing material for various applications ranging from future battery designs to filtration. This work investigated the possibility of using milled gasification biochar, derived from a 20 kW fixed-bed gasifier fueled with vine pruning pellets, as an addictive in the preparation of electrospinning solu-tions. This study outlined that solvent cleaning and the consequent wet-milling and 32 µm sifting are fundamental passages for biochar preparation. Four different polyacrylonitrile-biochar shares were tested ranging from pure polymer to 50–50% solutions. The resulting fibers were analyzed via scanning electron microscopy, and energy-dispersive X-ray and infrared spectroscopy. Results from the morphological analysis showed that biochar grains dispersed themselves well among the fiber mat in all the proposed shares. All the tested solutions, once carbonized, exceeded 97%wt. of carbon content. At higher carbonization temperatures, the inorganic compounds naturally showing in biochar such as potassium and calcium disappeared, resulting in an almost carbon-pure fiber matrix with biochar grains in between. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.