The separation of lanthanide and actinide elements belongs to one of the most challenging tasks of the separation science, due to a great similarity in their physical and chemical properties. The electrophoretic separation can be accomplished in the presence of suitable complex-forming agents, from which (x-hydroxyisobutyric acid (HIBA) has been used most often. In the most effective capillary electrophoretic mode - capillary zone electrophoresis (CZE) - a complete separation of lanthanide ions can be accomplished within a few minutes. Various electrophoretic methods can be relatively easily adopted for the determinations of individual lanthanide elements in certain kinds of technical materials, concentrates, precursors, etc., where the high speed and low costs of analysis characteristics of capillary electrophoresis (CE) may be advantageously exploited. Electrophoretic techniques may also be employed for speciation studies, especially for examinations of the behavior of actinides in the environment.