Bi-2-naphthol(BINOL) enantiomers were baseline resolved on HPLC network-polymeric chiral stationary phase (Kromasil CHI-DMB, based on O,O′-di(3,5-dimethylbenzoyl)N,N′-diallyl-L-tartaric diamide). The effects of the column temperature, the type and the concentration of the polar alcohol modifier in the binary mobile phase on the chiral resolution were examined. The separation value was 1.191 when V(hexane)∶V(2-propanol)=95∶5 was used as mobile phase at a flow rate of 1.0 mL/min at 25 ℃ with retention time being within 14 minutes. The mechanism of the chiral recognition was discussed with the calculated thermodynamic parameters. It is suggested that hydrogen bonding interaction between hydroxyl group of the solute and the CSP play important roles in chiral recognition. The chiral resolution is enthalpy-entropy driven and the enthalpy contribution is greater. 1,1′-Bi-2-naphthyl di-p-toluenesulfonate, 1,1′-bi-2-naphthyl diacetate and 1,1′-bi-2-naphthyl dicinnamate could not be resolved at experiment conditions used.