A simple and precise method was established for the simultaneous determination of daidzin and puerarin and the determination of daidzein in oriental pharmaceutical decoctions containing Puerariae Radix using high-performance liquid chromatography with tetra-n-heptylammonium bromide (THA) as an ion-pair reagent. Daidzin and puerarin were eluted within 45 min without interference with co-existing components using an ODS column and a mixture of 10 mM phosphate buffer (pH 6.5)-methanol (68:32) containing 5 mM THA as a mobile phase. Daidzein was eluted within 35 min without interference with co-existing components using an ODS column and a mixture of 10 mM phosphate buffer (pH 6.5)-acetonitrile (72:28 or 68:32) containing 5 mM THA as a mobile phase.