Three new hybrid organic/inorganic polymeric ligand-exchange chiral stationary phases were developed by radical chain transfer reaction and surface grafting on silica gel, and successfully used for the enantioseparations of DL-amino acids and DL-hydroxyl acids. The resolutions were achieved by using water containing 2.0 × 10-4 mol/L of CuAc2 as a mobile phase, column temperature of 40 ℃, flow rate of 1.0 mL/min and detection at UV 254 mn. The elution order of D-isomer before L-isomer was observed for all DL-amino acids resolved except DL-Pro.