We report a method to produce processable Pickering emulsions in which electrostatic heteroaggregation of oppositely charged fumed silica and alumina particles is exploited. The ability of weakly charged heteroaggregates to adsorb to the oil-water interface favors the formation of highly stable emulsions. A control over the microstructure and rheology of the Pickering emulsion is demonstrated by tuning parameters such as composition, pH, and total concentration of particles. The Pickering emulsions formed under optimal conditions are found to be gel-like and are excellent templates for the fabrication of porous ceramics. Furthermore, the porous mullite ceramic structure which has exceptional thermal and chemical resistance under harsh environments is obtained by drying and sintering of the emulsion template. The phase evolution, microstructure, and porosity of the resulting ceramic are characterized. © 2020 American Chemical Society.