Herein, 32 plastic pack belt (rope) samples were examined via X-ray fluorescence spectrometry. At the acquisition time of 80 s, the elemental composition was most stable. The function model was constructed by combining the multivariate statistical method. The ward’s method was selected as the clustering method. The square Euclidean distance was used as the measurement interval to describe the degree of affinity between the samples for hierarchical clustering. The 32 plastic pack belt (rope) samples were divided into four categories. The accuracy and reliability of the hierarchical clustering were tested via correlation between the samples and discriminant analysis, and the internal relationship between the contents of the sample elements was determined. In this experiment, 32 samples of plastic pack belts (ropes) were classified using the hierarchical clustering method, which promoted the application of pattern recognition technology for physical and chemical examination.