In this paper, we present the first enantioseparations using arabinose, ribose, ribodesose, lyxose, and fucose as chiral selector bonded to silica gel via 3-(triethoxysilyl)propyl isocyanate in HPLC. These chiral stationary phases possess good enantioseparation selectivity in the normal-phase mode, and there is a big chiral discriminating complementary. This work indicates that monosaccharides could soon become very attractive as a new kind of chiral stationary phase for HPLC.