For the courier plastic packaging bag evidence that often be extracted on the site, a method for rapid test analysis and sample classification was established. The inorganic elements in 41 samples of express plastic packaging bags from different express companies and different origins were analyzed by X-ray fluorescence spectrometry. The samples were classified according to the element contents of different samples, and the clustering analysis was carried out by using the hierarchical clusterand K-MEANS clustering. The samples were effectively distinguished from each other based on the inorganic element contents and their ratios of major elements derived from the tests. The samples were successfully clustered into 4 categories by hierarchical cluster method. The clustering results were examined by the K-Mean algorithm, and their grouping results were basically consistent, indicating that the clustering effect of the method was good. Using X-ray fluorescence spectrometry combined with cluster analysis to examine 41 samples, the results showed that the characteristics of various types of samples were obvious, with a high degree of differentiation, and could be achieved for different companies, different sources of express plastic packaging bags to distinguish. The method in the paper provided a certain theoretical reference for dealing with such physical evidence in public security work.