We report on the simple way of obtaining aligned poly(vinylidiene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers by electrospinning process. The collector drum rotation speed was adjusted to prepare well aligned PVDF-HFP nanofibers. The degree of alignment and the orientation of PVDF-HFP nanofibers can be significantly altered by varying the speed of collector drum rotation. The resultant PVDF-HFP nanofibers were systematically characterized. From the scanning electron microscopy data, it was found that the electrospun PVDF-HFP nanofibers were formed with well-aligned nature. The X-ray diffraction results revealed that the electrospun PVDF-HFP nanofibers with β-phase can be formed by the increased collector drum rotation speed. Overall, the collector rotation speed during the electrospinning process plays an important role in obtaining well-aligned and improved characteristics of PVDF-HFP nanofibers.