Polyacrylonitrile solutions in N,N-dimethylformamide (DMF) were electrospun into nanofibers by charging the polymer fluid in an electric field. Controlled experiments were performed using a needle type spinneret to investigate the effect of various electrospinning parameters on the percentage conversion of polymeric fluid into fibers and on fiber diameter obtained. It was found that when the polymeric fluid was continuously fed at a constant rate, application of a minimum electrospinning voltage (MEV) was necessary to "completely" convert the ejected fluid into nanojets to form nanofibers. Also, that the maximum amount of splitting or elongation that a polymeric fluid could undergo was primarily dependent on number of entanglements per chain in the fluid. This resulted in obtaining nanofibers with a particular diameter irrespective of the values of important electrospinning variables such as applied voltage, flow rates, and distance between the electrodes. On the other hand, MEV, necessary to obtain full conversion into nanofibers, was found to be strongly dependent on the spinning parameters and was unique for a given set of parameters. The significance of the MEV was evident from the fact that the square of the MEV, which is a measure of the electrical energy utilized by the system, was found to be directly proportional to the rate of formation of fiber surface area during the electrospinning process. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: 856-866, 2011