In order to respond to the national call for recycling of solid waste resources and adhere to the concept of green development, high-silicon waste silica fume was used as the main raw material, and CaO-Al2O3-SiO2 series glass-ceramics were prepared by the overall crystallization method. The crystal phase type and micromorphology of glass-ceramics were characterized by TG-DSC, XRD, SEM, and the physical and chemical properties of glass-ceramics were tested. The studies show that after 2 h nucleation at 900 ℃ and the crystallization temperature is 1 150 ℃ for 2 h, glass-ceramics with anorthite as the main crystal phase can be prepared. When the crystallization temperature continues to rise to 1 200 ℃, a small amount of bubbles appear in glass-ceramics, and internal defects appear, which results in the decline of crystallization effect and physical and chemical properties. The glass-ceramics prepared by this method have excellent mechanical properties, the flexural strength is 93.58 MPa, the Vickers hardness is 845.62 HV0.5, the bulk density is 2.88 g/cm3.