Recently, we have reported that syndiotactic polypropylene (sPP) fibrous membrane could be successfully prepared from a multi component solvent system via electrospinning at room temperature. The base solvent of multi component solvent system was cyclohexane. As demonstrated SEM images, the formation of rough surface morphologies and the microholes on electrospun sPP fibers were observed. In this study, we successfully prepared sPP nanofiber webs from a different base solvent was decalin. SEM study demonstrated that the sPP nanofibers prepared from decalin based solvent had smoother surface morphology unlike cyclohexane based solvent, suggesting that the surface morphology of electrospun sPP nanofibers depended on the boiling point of each solvent used. Moreover, to investigate the crystal and molecular structures of electrospun sPP fibers from a different solvent system (i.e., decalin and cyclohexane based solvents), WAXD and FT-IR analysis were carried out. The results showed that the different solvent systems caused the different surface morphologies but the crystal and molecular structure of the electrospun sPP fibers didn’t change.