Metal ions are essential for human beings at low concentrations but they are toxic or even carcinogenic at high concentrations. Many metallic ions are found in the environment in different species which are differentiated not only by their physicochemical forms but also by their diverse toxicities with respect to living organisms (speciation). CE has been used for metal ion speciation. The present review article describes the recent trends in metal ion speciation by CE. This article deals with the speciation of metal ions, optimization of the speciation (by independent and dependent variables), hyphenation of CE, validation of the methods, mechanisms of speciation, CE versus chromatography and conclusions.