This study used monocalcium aluminate (CaAl2O4,CA) for producing ceramic composites with duplex microstructures by hydration and gelation reactions of the aluminate, and compared the properties with those made by a die-pressing process of mixed powders. Densification of the composite was optimized. The microstructure of sintered bodies, the fracture strengths and toughness of the composites with and without thermal shocking was characterized by different techniques. Experimental results show that the green body with the addition of CA resulted glomerated platelets or uniform distribution of platy CA6 grains. The former, which appeared a duplex microstructure consisted of dense matrix and distributed clusters of CA6 platelets, performed an improvement on toughness and thermal shock resistance. Toughness mechanisms of samples with duplex microstructure are also investigated.