This study focused on the preparation of electrospun polystyrene (PS) nanofibers. Polystyrene solutions were prepared in single (dimethylformamide; DMF, dimethylacetamide; DMAc or tetrahydrofuran; THF) and mixed solvent (DMF/THF and DMAc/THF) systems prior to electrospinning. The effects of solution parameters, including PS concentration and solvent system on solution properties (e.g. conductivity and viscosity), appearance and diameter of polystyrene fibers were examined. The morphology of the as-spun fibers were carefully investigated using scanning electron microscopy (SEM). It was found that the average diameter of the as-spun fibers increased upon increasing PS concentration. Moreover, the morphology of the fibers significantly depended on the properties of the solvents. The obtained fibers were smooth without any beads and their diameters depended on the amount of THF in the mixed solvent and PS concentration. In summary, the smallest diameter (927±81 nm) and the narrowest fiber diameter distribution of PS nanofibers were obtained from 15% PS solution in DMF/THF (75/25).