Submicrometer spherical particles of mullite powder were synthesized by ultrasonic spray pyrolysis of emulsion and solutions, using tetra-ethyl-orthosilicate (TEOS) or silicic-acid and Al(NO3)3 · 9H2O as initial compounds. Crystallization of mullite phase was determined by differential thermal (DT), thermogravimetric (TG), infrared (IR), and x-ray analyses. The synthesis of mullite from TEOS emulsion occurs by crystallization of γ–Al2O3 (or Al, Si-spinel) from the amorphous phase and its subsequent reaction with amorphous SiO2, as well as by crystallization of pseudotetragonal mullite below 1000 °C and its subsequent phase transformation into orthorhombic mullite. In the powders produced from silicic acid solutions, synthesis of mullite occurs only by crystallization of γ–Al2O3 between 900 and 1000 °C and its further reaction with amorphous SiO2 between 1100 and 1200 °C. Particle formation mechanism depended directly on the initial emulsion or solution preparation, i.e., on the phase separation in the emulsion and on the silicic-acid crosslinking conditions.