Development of a new generation of electrospun polymeric materials designed to accomplish multi-performance in a bioinspired integrated system represents an important goal of the scientific research community. The major concerns in the medical therapy by the development of a new "construct" are based on a professional designing and understanding of the origin and physicochemical properties of the polymeric materials. It is well-known that almost all tissues and organs, i.e., skin, cartilage, and bone, etc., show a kind of similarity to nanosize fibrous structures. In this context, polysulfones promise to become such generation of nanofibrous scaffolds with attractive properties associated with biomedical applications. Therefore, the homogeneous solutions of the functionalized polysulfones, with a tunable density of quaternary ammonium functional groups (PSFQ), dissolved in N,N-dimethylformamide and 2-Methoxyethanol, were processed by electrospinning to create of polymeric scaffolds that can modulate cellular behavior. By analyzing the relationship between processable solution properties and morphological aspects, the results have shown that the morphology of formed fibers, with different forms and dimensions, could be attributed to the combined effects of the polymer solutions concentration, thermodynamic quality of the used solvents, and implicitly, the cumulative effects of electrostatic interactions, hydrogen bonding or association phenomena, as well as the process parameters. Thus, by investigation of the electrospun fibers morphology, the long, uniform and continuous fibers was visualized, with a wide distribution of diameters ranging from 0.65 μm to 2.40 μm, depending on the solvent used. Additionally, the antibacterial activity of PSFQ fibers against Gram-negative and Gram-positive bacteria has indicated the potential of these scaffolds for biomedical use.