In the work, microporous periclase-composite spinel ( Mg( Fe, Al)2O4 ) ceramics was successfully prepared using calcined MgO, Fe2O3 and Al(OH)3 as raw materials by in-situ decomposition synthesis. Meanwhile, the effects of raw material on its microstructures and properties were studied. The results show that when the periclase-composite spinel (Mg(Fe, Al)2O4 ) content is 0% (mass fraction, the same below), less neck connection form in the sample as well as the compressive strength is low. When the theoretical periclase-composite spinel (Mg(Fe, Al)2O4 ) content is 4% ~ 16% , the content of the liquid increases and the mass transport accelerates. Then, lots of neck connections form and the compressive strength is high. When the theoretical periclase-composite spinel ( Mg ( Fe, Al)2O4 ) content is 24% , the expansion amounts caused by the formation of composite spinel increase so the inter-particle pore size increases and the neck connections decrease. Therefore, the compressive strength of the sample decreases. When the theoretical periclase- composite spinel (Mg(Fe, Al)2O4 ) content is 12% ~ 16% , microporous periclase-composite spinel (Mg(Fe, Al)2O4 ) ceramics has excellent comprehensive properties, the apparent porosity of 22. 3% ~ 24. 6% , the bulk density of 2. 75 ~ 2. 80 g / cm3 , the compressive strength of 100. 6 ~ 123. 1 MPa.