The smelting slag obtained through iron collection from waste automobile three-way catalysts was used as a raw material to prepare microcrystalline glass through a one-step crystallization heat treatment. The phase composition and microstructure of the prepared glass were analyzed through X-ray diffraction and scanning electron microscopy–energy dispersive X-ray spectroscopy, respectively. Single-factor experiments were conducted to investigate the effects of crystallization temperature from 900 to 950 °C and crystallization time from 0.5 to 4 h on the physical and chemical properties of the microcrystalline glass. The results indicated that the optimum crystallization temperature and time for preparing microcrystalline glass with glass smelting slag through the proposed one-step crystallization heat treatment process were 950 °C and 3 h, respectively. Under these experimental conditions, the number of crystalline phases of the microcrystalline glass was high, the grains were mainly spherical and columnar particles, the sample structure was dense, and the best results were obtained: the density was 2.72 g/cm3, the water absorption was 1.55%, the porosity was 4.2%, the Vickers hardness was 618 HV, the acid resistance was 2.6%, and the alkali resistance was 0.04%. In addition, the results of the toxicity characteristic leaching procedure indicated that the leaching concentrations of heavy metals such as Zn, Cr, and Pb in the microcrystalline glass were lower than those in the base glass and were considerably lower than the acceptable limits. The microcrystalline glass obtained from final smelting slag through heat treatment can enhance the stabilization of harmful elements. The findings of this study can be applied to the treatment of bulk solid waste.