To establish a method for quality control samples for the poppy shell in solid compound spices. The spice matrix materials and the poppy shell were dried by microwave, mixed, pulverized,sieved, and then mixed again. After added with antagonist, the samples were dried, sieved, and mixed again.The homogeneity and stability of the samples were strictly examined.The concentrations of each chemical constituent in the samples were collaboratively analyzed using liquid chromatography-tandem mass spectrometry in 10 laboratories and then the uncertainty was assessed.The results showed that the characteristic values of the codeine, thebaine,morphine,papaverine,noscapine in these samples were (907±20.9), (918±18.4), (315±16.5), (171±12.6), (139±15.8)μg/kg respectively. The uniformity and stability was good. The methodology is suitable for verifying alkaloids in solid compound spices to control the quality.