Electrospinning of polystyrene (PS) and styrene-isoprene-styrene block copolymer (SIS) blends with different composition weight ratios was carried out with a mixed solvent, tetrahydrofuran (THF) and N, N-dimethylformamide (DMF) (80/20, v/v). Electrospun PS/SIS blend fibers were characterized using scanning electron microscopy. The results indicated that the presence of DMF resulted in a beneficial effect on fiber formation and greater electrospinnability of as-spun fibers. Furthermore, the morphological structure and diameters of as-spun fibers from PS and SIS blends were affected by the composition weight ratio and the solution properties. The fibers from 10 wt% solution exhibited the best mechanical properties compared to the fibers from other concentrations for the same composition, and increasing the SIS content one observes a vanishing of PS-related properties, while SIS-related properties emerges.