Integrated gasification combined cycle (IGCC) is a highly efficient method for producing electricity but discharges a byproduct in the form of a glassy slag, similar to other electricity generation operations. Several technologies for recycling IGCC slag have been developed thus far, although the results obtained are not promising or universally applicable. We quantitatively characterized an IGCC slag by using various testing methods, including an automated scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) system, to recognize its potential for recycling. The IGCC slag did not contain free CaO, and the absence of free lime would address a concern of volumetric expansion during hydration. Automated SEM-EDS analysis revealed that approximately 98% of the IGCC slag particles consisted of calcium-rich aluminosilicate materials. Obvious differences in the concentrations of Si, Al, and Ca between the amorphous phases and the average chemical bulk were recognized. The chemical composition of the amorphous Si-Al-Ca phases was similar to that of Class C fly ash, while the average bulk composition of the IGCC slag was in between that of Class C and Class F fly ashes. Considering this discrepancy, understanding the dissolution mechanism of the reactive amorphous fraction as well as an exact assessment of the reaction products based on the role of Ca in alkali-activated materials provides a new approach for the valorization of IGCC slag.