The growing awareness of the strong development of the toxicity of heavy metals upon their chemical forms has led to an increasing interest in the qualitative and quantitative determination of specific metal species. Speciation has therefore become an important topic of present-day analytical research. The development in the elemental speciation analysis by capillary electrophoresis (CE) is reviewed. Various CE separation modes and detection techniques applied are discussed. A comprehensive description of reported methods to date in CE speciation analysis including metals, metalloids and nonmetallic elements is demonstrated. Some examples are presented to demonstrate CE's ability to solve real-world speciation analysis with emphasis on the applications in biological and environmental samples. Further, some issues concerning the limitations and the future of CE with regard to speciation studies are also discussed.