Textured kaolinite and halloysite-based materials were shaped by tape casting in order to promote the alignment of clay particles along the tape casting direction and to investigate the structure evolution of these phyllosilicates during the dehydroxylation process. The crystallinity indexes HI and R2 of the starting kaolins (KRG and KCS) were determined and appeared close to values found for the well-ordered reference kaolin KGa-1b. The halloysite clay exhibited trimodal grain size distribution and tended to be less textured than KRG and KCS according to the (002) pole figures performed on green tapes. The constant heating rate derived kinetic parameters matched the expected range. We followed the dehydroxylation of kaolinite and halloysite through in situ high-temperature X-ray diffraction measurements at the ESRF synchrotron radiation source on the D2AM beamline. The dehydroxylation of these kaolinite and halloysite occurred between 425 °C and 675 °C for KRG and KCS and from 500 °C to 650 °C for halloysite. In addition, the evolution of the basal distance of kaolinite regarding the heat treatment temperature confirmed that the dehydroxylation process occurred in three steps: delamination, dehydroxylation, and formation of metakaolinite. The calculated coefficient of thermal expansion (CTE) along the c axe values were close to 17 × 10−6 °C−1 for kaolinite (KCS and KRG) and 14 × 10−6 °C−1 for halloysite.