Poly(vinyl alcohol) (PVOH) was electrospun using different methods to charge the polymer solution. A positive high voltage relative to the collecting electrode significantly increased the fiber deposition rate. Electron microscopy showed that approximately half of the increase in fiber mass was due to thicker fibers being deposited. The Current flowing from the grounded electrode was measured to determine the charge carried on the PVOH jet. This showed that for a positive voltage charging condition there is a much larger current and hence more charge carriers generated in the PVOH solution. As a result, more mass is ejected from the Taylor cone, implying that a positive voltage also produces longer fiber for a given time period. We also tested whether different substrate materials caused any variation when the charging conditions were changed. Statistically significant variation between substrates was only found when the substrate was an insulator and was expected to support a high-deposition rate. This confirms the view that the PVOH fiber arrives at the collecting electrode carrying a charge that must be neutralized, otherwise a repulsive charge will form where the fiber is deposited and some fiber will be lost to any alternative earth. In electrospraying, charge carriers are generated using associated redox reactions. Thus, for electrospinning a lack of symmetry in these reactions may result in the generation of different quantities of charge carriers in the PVOH solution and changes in the mass deposition rate of electrospun fiber. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 1729-1737, 2009