Capillary electrochromatography (CEC) is a hybrid separation technique that seeks to exploit the combined advantages of both capillary electrophoresis (high efficiencies) and HPLC (mobile and stationary phase selectivity). It is a technique with tremendous potential, especially in the pharmaceutical and biomedical fields. This study is devoted to the topic and presents reviews by leaders in the field on the theory and development of the technique and current and potential future applications.