The carbothermal reduction and nitridation has been used to synthesize composite ceramic powders from rice husk ash (RHA) with alumina addition of 0.02, 0.1, 0.5 and 1 (Al2O3/SiO2) respectively. The phase composition of products after calcining at high temperatures was almost sensitive to the Al2O3 content. The sequence of phase-formation except for SiC and Si3N4 with alumina addition was followed by Si2N2O→Si1.62Al0.38 N1.62O1.38→Si3Al3O3N5 for 1500 °C, and Si3Al3O3N5→AlN for 1550 °C. The results highlighted that effects of alumina impurity on the synthesis of composite ceramic powders from rich husk ash were significant.