This study was conducted to provide a quantitative understanding of the influence of the different solution and electrospinning variables on the morphology and the mean diameter of electrospun polystyrene nanofibers. In this regard, the effect of different solvents and ionic additives on the electrical conductivity, viscosity, and surface tension of the electrospinning solutions and thereby the morphology of nanofibers were examined. The results indicated that the morphology of the fibers is extremely dependent on the solvent’s properties, especially volatility and electrical conductivity, and the ionic characteristics of additives. Finally, to estimate the optimal electrospinning conditions for production of nanofibers with minimum possible diameter, modeling of the process was undertaken using the response surface methodology. Experimentally, nanofibers with the finest diameter of 169 ï¿œ 21 nm were obtained under the optimized conditions, and these could be considered promising candidates for a wide practical range of applications ranging from biosensors to filtration.