Basic insulating refractories were fabricated by the pressing route using dead-burned magnesia, pure calcined alumina, expanded perlite, and calcined waste serpentine as starting raw materials in four compositions from F1 to F4. Periclase and forsterite were major phases in F1 and F2 compositions, while spinel was also detected in the XRD patterns of F3 and F4 samples. Quantitative phase analysis showed that F4 sample sintered at 1450 °C has the highest forsterite content among all other samples. On the other hand, it has lower thermal conductivity compared to F1 to F3, and even lower than aluminosilicate IFBs with the same bulk density. It is concluded that forsterite is a highly insulating material, compared to periclase, corundum, periclase-spinel, aluminosilicates, such as mullite, etc.