Recently, the electrospinning technique has been explored as a natural and synthetic polymer processing tool due to its versatility and potential to generate complex structures at a nanoscale. In this work, non-woven nanofibrous mats were electrospun, with a structure resembling the extracellular matrix, for prospective biomedical uses. Poly (vinyl alcohol) (PVA) and cellulose acetate (CA) based electrospun nanofibrous meshes were prepared at different ratios 100/0, 90/10, 80/20 and 70/30 and characterized in terms of fiber diameter. The process was kept as green as possible by resorting to a combination of acetic acid and distilled water as solvents. Optimal conditions for PVA/CA processing were established at 29 kV, feeding rate of 0.8 mL/h and distance between needle and collector of 17 cm. These allowed for the most uniform fibers with the smallest diameters to be produced.