This review summarizes most of the recent developments in the preparation and application of polar stationary phases for CEC covering the literature published since the year 2004. These polar stationary phases have been adopted for separation of analytes by the modes of packing column CEC, open-tubular CEC (o-CEC) and monolithic column CEC. Currently, development of o-CEC using bionnolecules, such as protein and DNA, as the immobilized ligands is highlighted partly due to the simplicity of preparation. Furthermore, monolithic columns have been extended quickly, particularly inorganic materials-based monoliths, such as silica, zirconia, hafnium, etc., as an alternative to packed columns have been developed quickly.