Technical Abstract: Capillary electrophoresis (CE) is a relatively new method that has improved the ability to separate and characterize cereal proteins dramatically. Commercial CE instruments have only been available since 1990. Several modes of separation are possible but the simplest and perhaps the most commonly used is free zone capillary electrophoresis (FZCE). In FZCE, the proteins are injected into a capillary filled with buffer and separated, primarily, on the basis of differences in charge density. This paper reviews the development of FZCE methods applied to wheat, rice, and oat storage proteins. The changes in capillary inner diameter size, buffer types and additives have played a major part in improved separations. FZCE is clearly a valuable addition to protein characterization methods.