Abstract A novel carbonaceous SiC/mullite composite aerogel is derived from catechol-formaldehyde/silica/alumina hybrid aerogel (CF/SiO 2 /AlOOH) via polymer-derived ceramics route (PDCR). The effects of the reactants concentrations on the physicochemical properties of the carbonaceous SiO 2 /Al 2 O 3 aerogel and SiC/mullite aerogel are investigated. The mechanism of the textural and structural evolution for the novel carbonaceous SiC/mullite is further discussed based on the experimental results. Smaller reactants concentration is favorable to formation of mullite. Reactants concentration of 25% is selected as the optimal condition in considering of the mullite formation and bulk densities of the preceramic aerogels. Spherical large silica particles are also produced during heat treatment, and amorphous silica is remained after this reaction. With further heat treatment at 1400 °C, silicon carbide and mullite coexist in the aerogel matrix. The mullite addition decreases the temperature of SiC formation, when compared with the conventional methods. However, after heat treatment at 1450 °C, the amount of mullite begins to decrease due to the further reaction between carbon and mullite, forming more silicon carbide and alumina. The carbonaceous SiC/mullite can be transferred to SiC/mullite binary aerogel after carbon combustion under air atmosphere. The carbonaceous SiC/mullite has a composition of SiC (31%), mullite (19.1%), SiO 2 (14.4%), and carbon (35%). It also possesses a 6.531 nm average pore diameter, high surface area (69.61 m 2 /g), and BJH desorption pore volume (0.1744 cm 3 /g). The oxidation resistance of the carbonaceous SiC/mullite is improved for 85 °C when compared with the carbon based aerogel.