2,4,6-Triamino-1,3,5-trinitrobenzene (TATB) compounds are commonly used in high performance explosives because of their thermal stability and high detonation velocities compared to other materials. The insensitivity and mechanical properties are related to the stability of their crystalline structure. Crystallographic structure and structural defects evolution of TATB and TATB-based compounds were studied by X-ray diffraction for powders, molding powders, and pressed compounds, using Rietveld refinement. The effects of synthesis conditions, thermal treatments, coating and pressing operations on the structure of TATB compounds were evaluated. The results show that the pressing operation results in anisotropic crystallite size, leading to an increase of the structural defects density. It could be due to the anisotropic mechanical response of the TATB crystal under pressure, possibly plasticity. Finally, it is shown that increasing thermal treatment temperature on TATB powders decreases the structural defects density.