A syndiotactic polypropylene (sPP) fibrous membrane was successfully prepared from a multicomponent solvent system at room temperature. As demonstrated by SEM, the morphology of sPP was strongly dependent upon the environment, especially the ambient temperature during electrospinning. The crystal structure of electrospun sPP fibers exhibits a mixture of forms I and III, as determined by WAXD. It is hypothesized that the less stable form III crystals with trams-planar chains are induced in the electrospun sPP fibers due to rapid, stress-induced crystallization during the electrospinning process. To confirm the existence of a traps-planar conformation, FT-IR and Raman were employed. However, it was found that form I is the dominant crystal structure in electrospun sPP fibers.