Analytical methods for chiral compounds require a separation step prior to mass spectrometric detection. CE can separate enantiomers by the use of a chiral selector and can be hyphenated with MS. The chiral selector can be either embedded inside the capillary (electrochromatography) or added into the background solution (EKC). This review describes the fundamentals and highlights the recent developments (September 2009–May 2013) of chiral CEC and EKC with detection using MS. There were 20 research and more than 30 review papers during this period. The research efforts were driven by fundamental studies, such as the development of novel chiral selectors in electrochromatography and of advanced partial filling techniques in EKC in order to optimise separation. Other developments were in application studies, such as in food analytics and metabolomics.