The interest of micellar electrokinetic chromatography (MEKC) and microemulsion electrokinetic chromatography (MEEKC) for the resolution of four cardiac glycosides is demonstrated. First, the influence of some parameters on the resolution of the solutes in MEKC such as the concentration of the surfactant, pH, addition of organic modifiers and urea is discussed. Then, results are compared with those obtained in MEEKC using different microemulsion compositions. Results indicate that MEEKC possesses several advantages over MEKC for the separation of relatively hydrophobic compounds such as digitalic compounds. First, microemulsions allow a better manipulation of the migration time window and of the retention of the solutes. Moreover, efficiency is improved with shorter analysis time.