Electrospinning is a widely investigated and used technique for creating nano and microfibres which has a wide range of medical and pharmaceutical applications. For cell culturing and tissue engineering, it is a greatly investigated method because it resembles the extracellular matrix. Changing the electrospinning parameters we affect the properties of these systems to fine-tune it for our needs. To create a high porosity fibrous mesh for culturing different cells in a suitable three-dimensional way, we need to step forward from conventional electrospinning. In this paper, we are presenting a strategy involving the addition of inorganic salts to electrospinning solution to reproducibly synthesize nano and microfibrous fluffy 3D structures from polysuccinimide (a biocompatible and biodegradable polymer). Effect of different concentrations of LiCl, MgCl2 and CaCl2 on fibre properties are presented. Results show that the 3D structured fibrous meshes were produced in the presence of LiCl, MgCl2 or CaCl2 in a narrow concentration range. To understand the effect of salt on the resulting meshes characterization of the ion-ion and ion-solvent interactions were carried out using vibration spectroscopy and density functional theory calculation.