This review gives an overview of the recent developments and applications in the use of CE-mediated microanalysis for enzyme studies. The period covers mid-2011 until mid-2013. Both off-line and in-line enzyme assays with their applications using CE are described in this article. For the in-capillary enzyme reaction, the techniques using electrophoretically mediated microanalysis (EMMA) as well as immobilized enzyme reactor (IMER) are discussed. The applications include the evaluation of enzyme activity, enzyme kinetics, enzyme inhibition, screening of enzyme inhibitors, and the study of enzyme-mediated drug metabolism.