The invention provides a method of using a multi-energy spectrum X-ray imaging system for the identification of articles and the multi-energy spectrum X-ray imaging system for the identification of articles. The method comprises the following steps: identifying the application scene and/or prior information of the article; selecting a parameter mode suitable for the article from a plurality of parameter modes stored in the multi-energy spectrum X-ray imaging system according to the identified application scene and/or prior information; and identifying the article by using the selected parameter mode, wherein the plurality of parameter modes are acquired by optimizing the system parameters of the multi-energy spectrum X-ray imaging system under specific conditions in virtue of training sample databases targeted to a variety of different articles. The multi-energy spectrum X-ray imaging system provided by the invention is applicable to a variety of different application scenes and realizes the balance between the performance of the system and expenditure.