This review summarizes the variety of stationary phases that have been employed for capillary electrochromatography (CEC) separations. Currently, about 70% of reported CEC research utilizes C18 stationary phases designed for liquid chromatography, but an increasing number of new materials (e.g., ion-exchange phases, sol-gel approaches, organic polymer continuous beds) are under development for use in CEC. Novel aspects of these different materials are discussed including the ability to promote electroosmotic flow, phase selectivity and activity for basic solutes. In addition, new column designs (polymer continuous beds and silica-sol-gel monoliths) are described.