Common methods of polymer nanofiber production include phase separation, template synthesis, electrospinning, and centrifugal spinning. The electrospinning technique has attracted great interest among academic and industrial scientists because it is a very simple and effective approach to produce nanofibers, which are attractive for various applications in biomedical engineering, filtration, protective clothing, catalysis reactions, and sensors. In this study, we aimed to investigate the morphological differences between the aligned poly(vinyl alcohol) nanofibers obtained using the centrifugal jet spinning and modified electrospinning methods. The morphological changes were observed in detail by field emission scanning electron microscopy. The dependence of the nanofiber alignment on the applied voltage or rotational velocity during fabrication was investigated. Changes in these two parameters caused gradual changes in the nanofiber alignment and alterations in the morphology of the nanofibers.