Abstract: The determination of absolute configuration of chiral compounds is typically a prerequisite for various investigations. In the present study, a Chiralcel OD-RH column coated with cellulose tris(3, 5-dimethylphenylcarbamate)(CDMPC)was used to evaluate the capability of enantiomeric separation of chiral aryl alcohols with a reversed phase HPLC. Results showed that the chromatographic behaviors, in terms of elution order, were closely correlated with absolute configurations of the chiral aryl alcohols. Therefore, this simple HPLC method can serve as an alternative approach to facilitate the determination of absolute configurations of chiral aryl alcohols according to their elution orders. To rule out the possibility of false assignments, the underlying mechanism of this chromatographic behavior was further studied by IR and NMR. Hydrogen bondings between C=O, NH in the chiral cavity of CDMPC and different enantiomers were the key factor for the respective recognition and elution orders.