Due to a unique high efficiency in producing microfibers and nanofibers, centrifugal electrospinning that combines centrifugal spinning and electrospinning has attracted great interest in academic research and industrial manufacturing. This work is focused on the effects of various parameters of centrifugal electrospinning on the structure and properties of poly(vinyl pyrrolidone) fibers prepared by centrifugal electrospinning. The spinning parameters of interest included spinning voltage and rotation speed, and the characteristics of fibers included spinning productivity, jet trajectory, fiber morphology, fiber diameter, and fiber alignment. It was found that there was a competitive relationship between centrifugal force and electrostatic force during fiber formation. When only centrifugal force was applied, the obtained fibers mostly exhibited a circular distribution. When the electrostatic force began to increase, the fibers became increasingly uniform in morphology and showed a distribution in the vertical circumferential direction. The fiber alignment shows that the effects of these two factors on fiber alignment are competitive. The fiber yield shows that when the rotating speed is fixed at 1500 rpm, with the increase of voltage, the yield increases significantly and then increases slowly. The results suggest that centrifugal electrospinning can be favorable in the production of nanostructured fiber materials.