The present disclosure discloses a method of substance identification of an item to be inspected using a multi-energy-spectrum X-ray imaging system, the method comprising: acquiring a transparency related vector consisting of transparency values of the item to be inspected in N energy regions, wherein N is greater than 2; calculating distances between the transparency related vector and transparency related vectors stored in the system consisting of N transparency mean values of multiple kinds of items with multiple thicknesses in the N energy regions; and identifying the item to be inspected as the item corresponding to the minimum distance. The present disclosure is based on a multi-energy-spectrum X-ray imaging system, and proposes a method of substance identification by analyzing the multi-energy-spectrum substance identification issue.