Electrospinning is a straightforward method to produce micro/nanoscale fibers from polymer solutions typically using an operating voltage of 10 kV—30 kV and spinning distance of 10 cm—20 cm. In this paper, polyvinyl pyrrolidone (PVP) non-woven nanofibers with diameters of 200 nm—900 nm were prepared by low-voltage near-field electrospinning with a working voltage of less than 2.8 kV and a spinning distance of less than 10 mm. Besides the uniform fibers, beaded-fibers were also fabricated and the formation mechanism was discussed. Particularly, a series of experiments were carried out to explore the influence of processing variables on the formation of near-field electrospun PVP nanofibers, including concentration, humidity, collecting position, and spinning distance.