Capillary electromigration techniques have developed into significant analytical separation tools especially for enantioseparations. While CE can be considered a mature technique as documented by its wide applications, CEC is still in a developmental state despite many research efforts. The success of stereospecific CE separation methods is due to the high specificity and flexibility of the technique as well as the availability of many types of chiral selectors. Thus, numerous methods have been developed for the analysis of chiral compounds in chemical, biochemical, pharmaceutical, environmental, and forensic sciences. However, most reported applications deal with pharmaceuticals. The search for new chiral selectors also continued despite the fact that most applications were performed using cyclodextrins. Furthermore, CE has been combined with spectroscopic and molecular modeling studies in attempts to understand the interactions between chiral selectors and analytes. The present review focuses on recent examples of mechanistic aspects of capillary enantioseparations with regard to mathematical modeling of enantioseparations, investigations of the analyte‐complex structures as well as new chiral selectors and applications of chiral analyses by CE and CEC. It covers the literature published between January 2011 and August 2012.