Abstract: Taking the Baiyunebo tailing and fly ash as main raw material, the slag glass-ceramics were prepared by melting method. The effects of mass ratio of CaO to Al2O3 in raw materials on the structure and properties of the glass-ceramics were studued by differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM). The results show that the crystallization temperature of the base glass increased with the decrease of mass ratio of CaO to Al2O3. It could be found that the bending strength of the glass-ceramics first increased and then decreased with the decrease of mass ratio of CaO to Al2O3 and the bending property decreased because of the appearance of anorthite. The glass-ceramics had the best comprehensive properties when the mass ratio of CaO to Al2O3 was 4.5, the bending strength of the glass-ceramics was 164.9 MPa, the density was 2.98 g·cm-3, the acid-resistance was 92% and the alkali-resistance was 99%.