Chiral analysis is a very important issue in many aspects of health science, including the pharmaceutical, chemical, and cosmetic industries, as well as fields like food, environment, and several areas of forensic sciences. Among the available enantioselective separation techniques, capillary electrophoresis (CE) has emerged in the last decades thanks to numerous advantages. The miniaturization of the separation compartment has not only increased the analytical efficiency of the developed methods but also permitted the consumption of small amounts of sample, of solutions/solvents, and of possible chiral selectors. The focus of the present chapter is the application of enantioselective CE in forensic analyses. Descriptions of procedures in chiral CE methods, as well as results, will be given in detail, and troubleshooting will be recommended when available.