To use the potential heat of molten blast furnace slag completely, a CaO-Al₂O₃-SiO₂ system glass (MSG) was prepared from the molten industrial slag. The corresponding method proposed in this study utilized both slag and its potential heat, improving the production rate and avoiding the environmental pollution. Using appropriate techniques, an MSG with uniform color and superior performances was produced. Based on the experimental results and phase diagram, the chemical composition of MSG by mass is obtained as follows: CaO 27%–33%, SiO₂ 42%–51%, Al₂O₃ 11%–14%, MgO 6%–8%, and Na₂O+K₂O 1%–4%. Thermodynamic processes of MSG preparation were analyzed, and the phases and microstructures of MSG were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that alkali metal oxides serve as the fluxes, calcium oxide serves as the stabilizer, and alumina reinforces the Si-O network. XRD and SEM analyses show that, the prepared MSG displays the glass-feature patterns, the melting process is more complete, and the melt viscosity is lowered with an increase in calcium oxide content; however, a continuous increase in slag content induces the crystallization of glass, leading to the formation of glass subphase. The optimum content of molten slag in MSG is 67.37wt%. With respect to bending strength and acid/alkali resistance, the performance of MSG is better than that of ordinary marble.