This article is devoted to a brief review of the modelling of liquid membrane separation methods, such as emulsion, supported liquid membranes, film pertraction, and three-phase and multi-phase extraction. Mathematical models and comparative analyses of liquid membrane separations with different flow modes of contacting liquid phases are presented. A comparison of the processes of conventional and liquid membrane separations is carried out under the following assumptions: mass transfer is described by the traditional mass transfer equation; the equilibrium distribution coefficients of a component passing from one of the phases to another are constant. It is shown that, from the point of view of mass transfer driving forces, emulsion and film pertraction liquid membrane methods have advantages over the conventional conjugated extraction stripping method, when the mass-transfer efficiency of the extraction stage is significantly higher than the efficiency of the stripping stage. The comparison of the supported liquid membrane with conjugated extraction stripping showed that when mass-transfer rates on the extraction and stripping sides are different, the liquid membrane method is more efficient, while when they are equal to each other, both processes demonstrate the same results. The advantages and disadvantages of liquid membrane methods are discussed. The main disadvantages of liquid membrane methods—low throughput and complexity—can be overcome by using modified solvent extraction equipment to carry out liquid membrane separations.