Electrostatic jetting from a free liquid surface offers an alternative to conventional electrospinning in which jets are emitted from spinnerets. In this work we analyze a system in which a wire electrode is swept (in a rotary motion) through a bath containing a polymeric solution in contact with a high voltage, resulting in entrainment of the fluid, the formation of liquid droplets on the wire and electrostatic jetting from each liquid droplet. Solutions of polyvinyl pyrrolidone in ethanol were used as test systems to evaluate each stage of the process. The volumes of individual droplets on the wire were measured by photographic methods and correlated with the viscosity, density and surface tension of the liquid, and with system parameters such as electrode rotation rate and wire diameter. The local electric field in the absence of liquid entrainment was modeled using conventional electrostatics, and jet initiation was found to occur consistently at the angular position where the electric field exceeds a critical value of 34 kV/cm, regardless of rotation rate. Two operating regimes were identified. The first is an entrainment-limited regime, in which all of the entrained liquid is jetted from the wire electrode. The second regime is field-limited, in which the residence time of the wire electrode in an electric field in excess of the critical value is too short to deplete the fluid on the wire. The productivity of the system was measured and compared to the theoretical values of liquid entrainment. As expected, highest productivity occurred at high applied potentials and high rotation rates. (C) 2012 Elsevier B.V. All rights reserved.