Smart materials-based polyfunctional capillary coatings used as stationary or pseudostationary phases significantly increase the capabilities of the capillary electromigration methods and provide separation, analysis, and on-line concentration of ionic, hydrophilic, hydrophobic, and neutral analytes in one analytical cycle while implementing different separation mechanisms of the individual capillary electromigration methods. The review covers such topics as the use of micellar polymers, ionic liquids, oligosaccharides, metal-organic and covalent organic frameworks, molecularly imprinted polymers, nanoparticles, and other smart materials for the synthesis of capillary electrochromatography stationary phases and summarizes and comprehends existing approaches to the development of smart materials for electromigration techniques. The unique properties of smart materials are discussed in terms of implementing various modes of hydrophilic capillary electrochromatography and micellar electrokinetic chromatography, which significantly expands method's analytical limits. Particular attention is paid to the synergistic effect exhibited by the joint use of two or more smart materials in electrophoretic analysis. A special section is devoted to chiral electrophoretic and electrochromatographic separations in bioanalysis involving smart materials. © 2025 Elsevier B.V., All rights reserved.