AbstractThis review article addresses the developments and applications of capillary electromigration methods coupled on‐line with MS for chiral analysis. The multiple enantiomeric applications of this hyphenated technology are covered including chiral analysis of drugs, food compounds, pesticides, natural metabolites, etc. in different matrices such as plasma, urine, medicines, foods, etc. This work intends to provide an updated overview (including works published till September 2009) on the principal chiral applications carried out by CZE‐MS, CEC‐MS and MEKC‐MS, discussing their main advantages and drawbacks in all their different areas of application as well as their foreseeable development in the not too distant future.