Oligomeric N-substituted glycines or "peptoids" with α-chiral, aromatic side chains can fold into well-defined helical secondary structures.Here, we show for the first time that they can be developed as excellent chiral selectors for chromatographic enantioseparation.Using chloroacetyl chloride and (S)-(-)-α-phenylethylamine as submonomers, a series of peptoid oligomers with three to seven (S)-N-(1-phenylethyl)glycine (Nspe) units were synthesized and covalently bonded to the surface of silica gel.The enantiorecognition abilities of the peptoid chiral stationary phases (CSPs) were evaluated by high performance liquid chromatography (HPLC) and 1H NMR experiments.