Polyvinyl alcohol nanofibers were prepared by a needleless electrospinning technique using a rotating spiral wire coil as spinneret. The influences of coil dimension (e.g., coil length, coil diameter, spiral distance, and wire diameter) and operating parameters (e.g., applied voltage and spinning distance) on electrospinning process, nanofiber diameter, and fiber productivity were examined. It was found that the coil dimension had a considerable influence on the nanofiber production rate, but minor effect on the fiber diameter. The fiber production rate increased with the increased coil length or coil diameter, or the reduced spiral distance or wire diameter. Higher applied voltage or shorter collecting distance also improved the fiber production rate but had little influence on the fiber diameter. Compared with the conventional needle electrospinning, the coil electrospinning produced finer fibers with a narrower diameter distribution. A finite element method was used to analyze the electric field on the coil surface and in electrospinning zone. It was revealed that the high electric field intensity was concentrated on the coil surface, and the intensity was highly dependent on the coil dimension, which can be used to explain the electrospinning performances of coils. In addition, PAN nanofibers were prepared using the same needleless electrospinning technique to verify the improvement in productivity.