Capillary electrophoresis (CE) is an electromigration technique where a high electric field is applied for the generation of electrophoretic and electroosmotic mobilities. Due to the high voltage applied to the ends of the capillary and to the good heat dispersion, very high chromatographic efficiency and analytes resolution can be obtained. Conventional detectors are usually used in CE and CEC including UV and fluorescence. However mass spectrometry (MS) has also been coupled with these techniques. Hyphenation with MS can offer undoubted advantages over conventional detectors. Among them, are the higher sensitivity, the possibility to determine the mass of analytes, the characterization of the compounds, etc. In this review paper, the recent results obtained by coupling electromigration techniques with MS are presented. Some selected recent (2019–July 2022) applications employing CE-MS and CEC-MS are also discussed. • This review reports the main features of capillary electrophoresis and electrochromatography. • Coupling CE or CEC with mass spectrometry resolves problems related to sensitivity. • Advantages and disadvantages in CE-MS and CEC-MS have been discussed. • Some selected applications (2019–July 2022) have been presented and discussed.