In this study, two power supplies having positive/ground and negative/ground electrode output ends were used separately for electrospinning of polyacrylonitrile nanofibers. Depending on type of power supply and electrode connection, electrospinning led to different fiber diameters and deposition areas. The nozzle was connected to a high voltage end while the collector was grounded. Regardless of power supply used, finer fibers with a larger deposition area were obtained, compared to that using the same setup but with a reverse electrode connection. With an increase in the applied voltage, fiber deposition area, and productivity increased for all electrode connections. Grounded nozzles provide much better control over fiber deposition than the reverse electrode connections. Finite element modeling was used to analyze the electric field profile in the electrospinning zone. It was revealed that high electric intensity was mainly located in the part that was charged with a high voltage electrode, which could explain the differences in fiber diameter and deposition area.