The microscopic understanding of electrocoalescence of oil-in-water (O/W) emulsions stabilized by surfactant is very important to improve the efficiency of electrical demulsification. The behaviors of the coalescence of O/W emulsion stabilized by surfactant in the presence of a direct electric field and a pulsed electric field were explored by nonequilibrium molecular dynamics simulations. According to the simulated results, an electrical method is feasible to demulsify an O/W emulsion stabilized by a surfactant. The configuration and movement of the sodium dodecyl sulfate (SDS) were determined by interactions between SDS molecules themselves and between SDS and oil/water molecules along with the force exerted by the applied electrical field. Two droplets will coalesce into one when the strength of the electric field exceeds 0.4 V nm⁻¹. The SDS group can be broken up by an electric field larger than 0.6 V nm⁻¹. The point when interaction energy between the hexadecane molecules of the two droplets begins to decrease from zero is consistent with the time when the two oil droplets came in contact. The coalescence process can be completed if the two droplets have begun to coalesce, even after the electric field was removed. Otherwise, the coalescence process cannot be completed. To enhance the efficiency of the electrocoalescence of O/W emulsions, strength, frequency and duty ratio of the electric field have to be optimized according to the properties of the emulsion. This research will help us to figure out how electric fields promote the efficiency of electrocoalescence of O/W emulsions with surfactant.