In recent years, chemiluminescence (CL)-based detection coupled to capillary electrophoresis (CE) as separation technique has attracted much interest due to new advances in home-made configurations, sample-treatment techniques for application to real matrixes, development of a commercial instrument and use of miniaturization techniques to obtain micro total analysis systems incorporating CE separation and CL detection in microchips. We present some developments, key strategies and selected analytical applications of CE-CL since the year 2000 in diverse fields (e.g., clinical and pharmaceutical, environmental or food analysis).