Technical Abstract: High performance capillary electrophoresis (HPCE) is an analytical method that uses a voltage differential to accurately move solvents and solutes through a capillary. HPCE is a relative newcomer to the field of cereal chemistry, it utilizes small inner diameter capillaries as an anti-convective medium in place of slab-gels. Due to the small inner diameter of those capillaries (typically 50 to 100 m) high voltages can be used, resulting in rapid, high resolution separations. Combining the high voltages (up to 30 kV) with isoelectric buffers and buffers varying in ionic strength, complex mixtures can be separated in minutes. Like traditional slab-gel electrophoresis, HPCE can operate in several modes. Methods for two modes have been developed for separating wheat proteins; free zone capillary electrophoresis (FZCE), and sodium dodecyl sulfate capillary electrophoresis (SDS-CE). This chapter describes the HPCE separations of gluten monomers. It summarizes numerous reports that describe such studies; with references to more comprehensive reviews and provides protocols for these separations. HPCE is a superb tool as it is complementary and often superior to previous methods for characterization of complex cereal proteins.