Mullite and mullite–alumina ceramics materials with dominance of the mullite phase are used in different areas of technology and materials science. Porous mullite ceramics materials can be used simultaneously as refractory heat insulators and also as materials for constructional elements. The purpose of this work was to investigate the WO3nanoparticle influence on the evolution of the aluminum tungstate and zircon crystalline phases in mullite ceramics due to stabilization effects caused by different microsize ZrO2and WO3. The use of nano-WO3prevented the dissociation of zircon in the ceramic samples with magnesia-stabilized zirconia (MSZ), increased porosity by approximately 60 ± 1%, increased the intensity of the aluminum tungstate phase, decreased bulk density by approximately 1.32 ± 0.01 g/cm3, and increased thermal shock resistance by ensuring a loss of less than 5% of the elastic modulus after 10 cycles of thermal shock.