In recent years electrowetting-on-dielectric (EWOD) has become an effective tool to control partial wetting. EWOD uses the liquid–solid interface as part of a capacitive structure that allows capacitive and interfacial energies to adjust by changes in wetting when the liquid–solid interface is charged due to an applied voltage. An important aspect of EWOD has been its applications in microfluidics in chemistry and biology and in optical devices and displays in physics and engineering. Many of these rely on the use of a liquid droplet immersed in a second liquid due to the need either for neutral buoyancy to overcome gravity and shield against impact shocks or to encapsulate the droplet for other reasons, such as in microfluidic-based DNA analyses. Recently, it has been shown that nonwetting oleophobic surfaces can be forcibly wetted by nonconducting oils using nonuniform electric fields and an interface-localized form of liquid dielectrophoresis (dielectrowetting). Here we show that this effect can be used to create films of oil immersed in a second immiscible fluid of lower permittivity. We predict that the square of the thickness of the film should obey a simple law dependent on the square of the applied voltage and with strength dependent on the ratio of difference in permittivity to the liquid-fluid interfacial tension, Δε/γLF. This relationship is experimentally confirmed for 11 liquid–air and liquid–liquid combinations with Δε/γLF having a span of more than two orders of magnitude. We therefore provide fundamental understanding of dielectrowetting for liquid-in-liquid systems and also open up a new method to determine liquid–liquid interfacial tensions.