A calculation method for a dual-energy X-ray imaging system is provided. The calculation method for the dual-energy X-ray imaging system includes the following steps. A plurality of material attenuation coefficient ratio of the dual-energy projection image are established according to the reference materials with known material characteristics. The effective atomic number of each reference material and the material attenuation coefficient ratio are used to establish a calibration data set. A rational polynomial approximation method is adopted to obtain the characteristic model related to the material attenuation coefficient ratio of the reference material and the effective atomic number of the reference material. The material attenuation coefficient ratio of the dual-energy projection image of unknown material is established. The material attenuation coefficient ratio of the unknown material is substitute into the characteristic model to obtain the effective atomic number corresponding to the unknown material.