In the study presented, the micro-emulsions are generated using the effects of electrochemical instability and surface tension drop at the polarized liquid/liquid interface. Polarization of the oil/liquid interface is studied in various aqueous systems including electrolytes and water-based solutions of cationic, anionic, zwitter-ionic and non-ionic surfactants. The physical features of the obtained emulsions, such as hydrodynamic flow patterns, droplets size distribution, and emulsion organization are described. The efficacy of different electrode configurations is also evaluated. Both theoretical model of the liquid/liquid interface polarization and experimental data obtained from various emulsification regimes are presented.