Objective:To establish a high performance liquid chromatography-photodiode array (HPLC-PDA) method for the simultaneous determination of five effective components (atractylenolideⅠ,atractylenolide Ⅱ,atractylenolide Ⅲ,albiflorin and paeoniflorin),detect their contents in Baizhu (Atractylodis Macrocephalae Rhizoma),Baishao (Paeoniae Radix Alba),couplet medicines and compound recipe (Tongxie Yao Recipe), and provide scientific basis for research on effects of compatibility on chemical components. MethodsThe separation was performed on a Thermo Fisher C,18, column (4.6 mm×150 mm,5 μm) by gradient elution of acetonitrile (A)-water (B) as the mobile phase at flow rate of 1 ml·min-1,with running time of 32 minutes and column temperature at 30 ℃. The detection wavelength was set at 222 nm for atractylenolideⅠand Ⅲ,278 nm for atractylenolide Ⅱ and 232 nm for albiflorin and paeoniflorin. The volume of sample injection was 10 μl.  Results:Linear investigation on detection results was performed by linear regression with peak area (Y) and concentration (X). The linear ranges of atractylenolideⅠ,Ⅱ,Ⅲ,paeoniflorin and albiflorin were at 0.008 0-0.320 0 μg (r,1,=0.999 9),0.004 1-0.160 0 μg (r,2,=0.999 8),0.210 0-0.840 0 μg (r,3,=0.999 7),1.750 0-70.000 0 μg (r,4,=0.999 8),1.000 0-40.000 0 μg (r,5,=0.999 6),respectively. The sample recovery test,precision test and repeatability test performed well. The stability test verified the good stability within 24 hours,which meant that the results were accurate and reliable. The contents of the five effective ingredients in single drug,couplet medicines and compound recipe were paeoniflorin ,>, albiflorin ,>, atractylenolide Ⅲ ,>, atractylenolideⅠ ,>, atractylenolide Ⅱ. Compared with the single drug,the contents of atractylenolideⅠ,Ⅱ and Ⅲ were increased after the compatibility of Baizhu and Baishao,but the contents of paeoniflorin and albiflorin were decreased. For the comparison between the couplet medicines and compound recipe,the content of atractylenolideⅠin the couplet medicines was obviously higher than that in the compound recipe,and the contents of atractylenolide Ⅱ,atractylenolide Ⅲ,paeoniflorin and albiflorin in the couplet medicines were obviously lower than those in the compound recipe.  Conclusion:This method can be used for the quality control of single drug,couplet medicines and compound recipe. Through the comparison of contents of effective ingredients in single drug,couplet medicines and compound recipe,it suggests the impacts of compatibility on effective ingredients of drugs.