We have investigated a possible method of synthesizing carbon-free, nano-silicon nitride–silicon carbide (Si 3 N 4 /SiC) powders from the waste silica fume for the first time, using the integrated mechanical and thermal activation (IMTA) process. This novel process results in the formation of nano-Si 3 N 4 /SiC powders at 1465°C with crystallite sizes as small as 45nm. In order to synthesize carbon-free nano-Si 3 N 4 /SiC powders, two different approaches, one using the H 2 gas and the other using air, have been studied for their effectiveness in removing the free carbon present. It is found that the H 2 treatment is not very effective although both Si 3 N 4 and SiC are stable during the H 2 treatment. In contrast, removing the free carbon using air is effective, and the limited oxidation of nano-Si 3 N 4 and SiC can be achieved if the air treatment is terminated soon after the free carbon is eliminated. This study has provided a clear pathway and understanding for effectively synthesizing carbon-free, nano-Si 3 N 4 /SiC powders from the silica fume.