The separation of immiscible liquids is critical in many industrial processes, such as water treatment, different extraction processes, the petroleum industry, food production, and medicine. This work provides an overview of present research on the separation of liquid mixtures. A brief summary of the thermodynamic basis is provided, covering phase equilibrium, phase diagrams, and thermodynamic properties of phases. Additionally, the fundamentals of dispersion, necessary for discussing liquid–liquid separation, are presented. Subsequently, different liquid–liquid separation methods are discussed, highlighting their advantages and limitations. These methods include decanters, coalescers, centrifugal separators, membranes and electro-coalescers for liquid–liquid separation. Phase properties, dispersion formation, and time and space constraints specify the most efficient separation method. Phase recycling is also briefly discussed as a method to reduce the environmental impact of liquid–liquid extraction with subsequent phase separation. In summary, liquid–liquid separation methods are compared and future perspectives of liquid–liquid separation are discussed.