Human tooth is a complex bioceramic composite, which consists of enamel, dentin and the interface, the dentin–enamel junction (DEJ). The crystal properties and ultrastructure of the inorganic phase through the thickness of healthy human molar teeth were investigated using X-ray microdiffraction (μXRD), electron diffraction and transmission electron microscopy (TEM) techniques. The XRD data were analysed using the Le Bail profile fitting approach. The size and the texture of the crystallites forming enamel and dentin in the crown part of teeth were measured using both techniques and then compared. Results showed that the thickness of dentin crystallites was found to decrease towards the DEJ, whereas the thickness of the enamel crystallites increased from the DEJ towards the outer layers. It was demonstrated that enamel exhibited an increase of texture in 002 lattice planes from the DEJ towards the outer layers. Texture was also detected in 102 lattice planes. The texture effect in 002 planes at the scale of less than 1 μm was also demonstrated in dentin. The variation of lattice parameters as a function of the position within the thickness of dentin and enamel was also observed. The values of the nonuniform microstrain in the dentin and enamel crystallites were from 1.40 × 10−6% to 4.44 × 10−5%. The good correlation between XRD and TEM indicated that μXRD is a useful technique to study crystallography and microstructure of heterogeneous enamel and dentin. The observed gradient characteristics of texture and crystallite size in enamel and dentin maybe an evolutionary outcome to resist wear and fracture, thereby contributing to the excellent mechanical properties of teeth.