In this study, crystal orientation and polymorphism formation in electrospun poly(vinylidene fluoride) (PVDF)/polyacrylonitrile (PAN) blend fibers after melt-recrystallization were studied. To achieve uniform alignment of electrospun fibers, mechanical stretching was applied to the as-spun nonwoven fibers at 110 °C. Pure ferroelectric β-PVDF crystals in the PAN matrix were achieved, and both polar β-PVDF and polar PAN crystals oriented with their chain axes parallel to the fiber axes. After melt-recrystallization of PVDF, a significant amount of ferroelectric β crystals was retained in addition to the formation of nonpolar α crystals. A polarized Fourier transform infrared study showed that the degree of orientation of ferroelectric β-PVDF crystals was higher than that of nonpolar α crystals, suggesting that the β-PVDF crystals should form at the PVDF/PAN interfaces because of strong dipolar and hydrogen bonding interactions between vinylidene fluoride and acrylonitrile units. The nonpolar α-PVDF crystals should form in the center of PVDF domains.