The term riboflavin binding proteins (RfBPs) is applied to several molecular species that play the important role of vitamin delivery to the developing embryo, thus becoming essential for the survival of the fetus. In addition to this physiological significance, these proteins have recently been found to be successful chiral selectors. In this review, the authors address the use of such proteins, both as columns for high performance liquid chromatography (HPLC) and as additives in capillary electrophoresis (CE), for the enantioseparation of several racemic drugs.