Abstract: Using Baiyun Ebo fluorite tailings and Baogang steel blast furnace slag as the main raw materials, a certain amount of quartz sand and borax were added to prepare glass-ceramics. The influence of raw material ratio and preparation process on the radioactivity of glass-ceramics was studied. Using a low background multi-channel gamma spectrometer, radioactive nuclide detection was carried out on various raw materials and glass-ceramics products. Based on the radioactive indicators of each raw material and the basic glass formula, the radioactive indicators of glass-ceramics products were predicted by calculation according to the principle of linear superposition. The research results show that during the process of gradually changing the mass ratio of fluorite tailings to blast furnace slag from 1∶9 to 9∶1 in the raw materials, with the increase of fluorite tailings ratio, the internal irradiation index of glass-ceramics shows a gradually decreasing trend, and the external irradiation index shows a gradually increasing trend. The preparation process basically does not affect the internal and external irradiation index of glass-ceramics; the relative errors between the predicted and detected values of the internal and external irradiation indices are controlled within 16% and 10%, respectively. The measurement relative error ranges of the internal and external irradiation indices are 9% to 13% and 7% to 11%, respectively, which can be used as an effective means of predicting product radioactivity. When the mass ratio of Baiyun Ebo fluorite tailings to Baogang blast furnace slag is 1∶9, 2∶8, and 3∶7, the glass-ceramic meets the B-class decoration material standard. When the mass ratio of Baiyun Ebo fluorite tailings to Baogang steel blast furnace slag is 4∶6, 5∶5, and 6∶4, the glass-ceramic meets the C-class decoration material standard. However, the radioactive isotopes of 7∶3, 8∶2, and 9∶1 glass-ceramic exceed the standard and cannot be used as building decoration materials, providing basic information and theoretical basis for the green and high-value utilization of solid waste from Baiyun Ebo mine selection and smelting.