Kaolin'' is a major raw material for the fabrication of conventional ceramics. In this work the authors have investigated the thermal phase transformation of mullite from two different types of kaolin (kaolinite and halloysite), with or without alumina matrix constraint, during heating up to 1500 1C and then cooling using in situ neutron diffraction. Mullitization was initiated upon heating to 1200 1C for all specimens and followed spinel formation at 1100 1C. Above this temperature, however, evolution of the main phases, i.e., mullite, cristobalite and corundum, was influenced by the presence of impurities, initial type of silica, and alumina constraint. The relative amount of mullite was largest for the pure kaolinite specimen, particularly during heating, and this was attributed to the presence of a glassy phase. However, kaolinite with alumina suppressed the crystallization of cristobalite from the glassy phase upon cooling due to a reaction between alumina and amorphous silica, consequently resulting in an amount of mullite as for the pure kaolinite specimen (approximately 65 wt%). Halloysite was less active in terms of mullitization due to the lower level of initial impurities and greater amount of cristobalite, particularly for the alumina-constrained specimen. However, the final amount of mullite derived from the pure halloysite specimen was similar to that as from the kaolinite specimen.