The effect of microwave radiation on the nucleation and crystallization of tailing-based glass-ceramics was investigated using a 2.45 GHz multimode microwave cavity. Tailing-based glass samples were prepared from Shandong gold tailings and Guyang iron tailings utilizing a conventional glass melting technique. For comparison, the tailing-based glass samples were crystallized using two different heat-treatment methods: conventional heating and hybrid microwave heating. The nucleation and crystallization temperatures were determined by performing a differential thermal analysis of the quenched tailing-based glass. The prepared glass-ceramic samples were further characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, thermal expansion coefficient measurements, and scanning electron microscopy. The results demonstrated that hybrid microwave heating could be successfully used to crystallize the tailing-based glass, reduce the processing time, and decrease the crystallization temperature. Furthermore, the results indicated that the nucleation and crystallization mechanism of the hybrid microwave heating process slightly differs from that of the conventional heating process.