Capillary electrophoresis is a powerful analytical technique which is increasing in utility in the pharmaceutical industry. It is used as an alternative or complementary technique to HPLC due to its high efficiency, speed of analysis, reduction in solvent and sample consumption, and low operating cost compared to HPLC methodology. Various modes have been developed and used for pharmaceutical analysis including capillary zone electrophoresis, non‐aqueous capillary electrophoresis, micellar electrokinetic capillary electrophoresis, capillary gel electrophoresis, capillary isotachophoresis, chiral capillary electrophoresis, and capillary electrochromatography. This review summarizes the principles and gives recent pharmaceutical analysis applications used for each mode of capillary electrophoresis. The review will also describe recent developments for enhancing concentration limits of detection.