The influence of calcined alum on the hydration process, the structure and intensity of hardened anhydrite, the degree of solution supersaturation, and other properties are investigated by determining setting time, hydration rate and hydration temperature increases in combination with analyzing the microstructure and intensity of hardened paste. The alum action mechanism also is revealed. The results indicate that calcined alum is a highly active excitant for anhydrite. Calcined alum can reduce setting time, increase the hydration process and intensity of anhydrite, and refine crystals. Calcined alum improves the hydration and solution performance of anhydrite and sulfate radical concentration. This subsequently raises the degree of dihydrate gypsum supersaturation. Anhydrite hydration and solution, and the spontaneous homogeneous nucleation and growth of dihydrate gypsum crystals are all accelerated.