Andalusite is easily converted to mullite and silica on heating. A better understanding of the mullitization mechanisms provides new information on use of this mineral in refractory castables. By using specific particle-size distributions for andalusite-based high-alumina castables, the primary mullite formation can be effectively enhanced by a secondary mullite reaction within castables matrices. The influence of ultrafine andalusite grains on thermomechanical properties of specimens is underlined by testing hot modulus of rupture in combination with mineralogical and microscopic analyses. The results demonstrate that andalusite has great promise as a component of high-alumina no-cement- or ultra-low-cement-containing castables.