Abstract: In order to strengthen the supervision of solid waste at ports and effectively curb the illegal flow of solid waste into China，a batch of copper-containing materials controlled by customs due to abnormal appearance were taken as cases，and the solid waste properties of the materials were identified by Xray fluorescence spectroscopy and X-ray diffraction. The results show that the samples mainly contain iron， sulfur，silicon，calcium，copper，zinc and other elements. The main phases of the sample are pyrite，sphalerite，ferrous sulfide，zinc and iron sulfide，gypsum，arsenopyrite，chalcocite，hematite，jarosite，quartzite，barite，jarosite and other components. Based on the appearance and physical and chemical properties of the samples，combined with the relevant literature and research results，it is concluded that the samples are derived from natural copper ore，iron ore，zinc ore and iron-zinc polymetallic ore，without solid waste， which provides a scientific basis for customs import supervision and effective utilization of resources.

Key words: solid waste identification, X-ray fluorescence spectrometer, X-ray diffractometer, polyme? tallic ore