The aluminate cement clinker was successfully synthesized from starting materials of barium carbonate, alumina and calcium carbonate by designing mineral phase composition sintered at different temperatures. The formation mechanism of cement clinker was investigated by XRD and SEM. The results show that BaAl2O4 is mainly formed at relatively low temperatures, and then CaAl2O4 obviously increases with the increase of temperature in forming solid solution of BaAl2O4 and CaAl2O4. In addition, there exists a small amount of Ca12Al14O33, CaAl2O4 and Ca3Al2O6 .in cement clinker. BaAl2O4 is mostly present in the shape of puncheon, and solid solution of BaAl2O4 and CaAl2O4 is developed into hexagon and round crystals.