The supramolecular interaction of BPO and ß-CD has been studied by spectrophtometry. The mechanism of the inclusion was studied. The results showed that ß-CD react with BPO to form a 2:1 or 1:1 host-guest complex.The ß-CD reacts with benzoic acid to form a 1:1 host-guest complex after the BPO was reduced by hydroxyl ammonium chloride.Based on the enhancement of the absorbance of BPO produced through complex formation, a spectrophotometric method for determination BPO in bulk aqueous solution in the presence of ß-CD was developed. A linear relationship between the absorbance and BPO concentration was obtained in the range of 0.2~50 μg.ml-1. The proposed method was used to determine the BPO in the flour with satisfactory results. The principal advantage of the proposed method is its excellent selectivity based on molecule recognition of ß-CD and simple.