Abstract: Electrokinetic transport near charged interfaces is a typical multi-physical, cross-scale phenomenon. The charged effects and electrokinetic transport phenomena at immiscible liquid-liquid interfaces have been studied for over a century and have gradually gained widespread attention in recent years. Examples include interfaces of immiscible electrolyte solutions, self-propelled droplets, and digital microfluidics, providing new strategies for the active control of multiphase flow and mass transfer systems at micro- and nano-scales based on interfacial electrokinetic transport. Compared to solid-liquid interfaces, liquid-liquid interfaces, as multiphase soft diffuse interfaces, possess characteristics such as finite thickness, easy mobility, ion adsorption capability, and ion permeability. Their electrokinetic transport behavior is linked to fields such as membrane science, electrochemistry, physical chemical hydrodynamics, and electro-coupled hydrodynamics, gradually forming an interdisciplinary field—electrokinetic multiphase hydrodynamics. This review will outline the fundamental characteristics of charged liquid-liquid interfaces and the mechanisms of electrokinetic transport in typical scenarios, showcasing the rich possibilities and broad research prospects in applied fundamental research.