The review presents a comprehensive survey of recent developments of high-performance capillary electromigration methods, zone electrophoresis, ITP, IEF, affinity electrophoresis, EKC and electrochromatography, and their application to analysis, preparation and physicochemical characterization of peptides. New approaches to the theoretical description and experimental investigation of electromigration properties of peptides, and to methodology of their separations, such as sample preparation, adsorption suppression, EOF control and detection, are described. New developments in particular CE and CEC modes are reported and several types of their applications to peptide analysis are presented: conventional qualitative and quantitative analysis, determination in biomatrices, monitoring of chemical and enzymatical reactions and physical changes, amino acid and sequence analysis, and peptide mapping of proteins. Few examples of micropreparative peptide separations are shown and capabilities of CE and CEC techniques to provide important physicochemical characteristics of peptides are demonstrated.