A clear understanding of the solid-state reaction of kaolinite (Kln), quartz (Qtz), and sodium carbonate (Na2CO3) is of great significance for the process optimization of coal gangue calcined with Na2CO3. In this work, a comparative study of the isothermal solid-state reaction systems of Kln–Na2CO3 and Kln–Qtz–Na2CO3 was performed by means of X-ray diffraction (XRD), scanning electron microscope, and energy dispersion spectroscopy (SEM-EDS). The results showed that the calcined products both for these reaction systems mainly contain different kinds of sodium aluminum silicates (e.g., NaAlSiO4, Na1.55Al1.55Si0.45O4, and Na1.95Al1.95Si0.05O4) and various kinds of sodium silicates (e.g., Na2Si3O7, Na2SiO3, and Na6Si2O7). The mass percentage of Na2CO3 played a key role in the phase transformation, determining the Na/Al/Si molar ratio of the formed sodium aluminum silicates. Compared with the reaction system of Kln–Na2CO3, the existence of Qtz inhibited the formation of sodium aluminum silicates in the reaction system of Kln–Qtz–Na2CO3. It should be noted that the formed phases both for these reaction systems were slightly different from that of the thermodynamical calculated results of Na2O–SiO2–Al2O3 using FactSage™ software. According to both the experimental and calculated results, a reasonable batching area for coal gangue activation was proposed that the addition of Na2CO3 should be in the range of 20–50% of the total mass of Kln, Qtz, and Na2CO3.