Abstract: Carbon nanomaterials have been widely applied in analytical science, life science, material science, environmental science and other fields due to the unique nano-structure, large specific surface area, strong thermal stability, good electrical conductivity and excellent adsorption properties. In this article, the recent advance of carbon nanomaterials as novel stationary phases of capillary electrochromatography(CEC) in the past five years, including the CEC categories, separation mechanism, preparation methods of chromatographic column and their advantages and disadvantages, structure and properties of carbon nanomaterials(graphene, carbon nanotubes, graphene oxide, reduced graphene oxide, fullerenes), application of carbon nanomaterials as CEC stationary phases and separation mechanisms is reviewed. And the future perspectives of carbon nanomaterials as chromatographic stationary phases are also outlined.