The oriented external electric field (OEEF) promoted phase transfer catalysis (PTC) reaction is reported for the first time. It was demonstrated experimentally that an OEEF can act as promoter or inhibitor for the phase transfer hydrogenation of acetophenone depending on its direction. Organic solvents showed differing influences on the reaction, attributed to different electrical conductivities. A non-linear dependence of product yield on OEEF potential was also discovered. This work presents a methodology for promoting PTC reactions in the absence of a chemical phase transfer agent and shows promise for significantly improving the performance of organic reactions in biphasic liquid systems.