Solid polymer electrolytes (SPEs) are the best choice to replace liquid electrolytes in supercapacitors, fuel cells, solar cells and batteries. The main challenge in this filed is the ionic conductivity and thermal stability of SPEs which is still not up to mark, therefore more investigations are needed to address these issues. In this study, PVA/salt based SPEs was fabricated using both solution cast and electro-spinning methods to probe the effect of different salts such as (NaCl, KCl and KI) and their concentrations on the ionic conductivity. Scanning electron microscopy (SEM) x and Fourier Transform Infra-Red (FTIR) have been employed to study the morphology as well as the different functional groups of SPEs, respectively. It was noted that small addition of NaCl, KCl and KI salts in SPEs dramatically increased the ionic conductivity to 5.95×10−6, 5.31×10−6 and 4.83×10−6 S/cm, respectively. Importantly, the SPEs obtained with NaCl via electro-spinning have higher ionic conductivity (5.95×10−6 S/cm) than their casted SPEs (1.87×10−6 S/cm). Thermal stability was also studied at two different temperatures i.e. 80 °C and 100 °C. The weight loss percentage of electrospun SPEs have zero percent weight loss than the solution based SPEs. The combined results clearly indicated that the nature of salt, concentration and fabrication process play a vital role in the ionic conductivity. Also, the NaCl salt with low molecular weight at low concentrations shows an enhanced ionic conductivity.