Abstract: The mineral transition and formation mechanism of calcium aluminate compounds in CaO−Al₂O₃−Na₂O system during the high-temperature sintering process were systematically investigated using DSC−TG, XRD, SEM−EDS, FTIR, and Raman spectra, and the crystal structure of Na₄Ca₃(AlO₂)₁₀ was also simulated by Material Studio software. The results indicated that the minerals formed during the sintering process included Na₄Ca₃(AlO₂)₁₀, CaO·Al₂O₃, and 12CaO·7Al₂O₃, and the content of Na₄Ca₃(AlO₂)₁₀ could reach 92wt% when sintered at 1200°C for 30 min. The main formation stage of Na₄Ca₃(AlO₂)₁₀ occurred at temperatures from 970 to 1100°C, and the content could reach 82wt% when the reaction temperature increased to 1100°C. The crystal system of Na₄Ca₃(AlO₂)₁₀ was tetragonal, and the cells preferred to grow along crystal planes (110) and (210). The formation of Na₄Ca₃(AlO₂)₁₀ was an exothermic reaction that followed a secondary reaction model, and its activation energy was 223.97 kJ/mol.