Ordered mesostructured mesoporous materials, combining nano-organization with atomic disorder, are both attractive and challenging objects of investigation by X-ray and neutron diffraction. The development of diffraction mesostructure analysis methods and their applications in studies on structural characterization, formation processes and physisorption phenomena in these advanced materials are summarized in this tutorial review. The focus here is on the techniques that allow extracting mesostructure parameters and peculiarities of density distribution in the materials from the Bragg reflection positions and intensities. The investigations of mesoporous silicates, their nonsilica replicas and composites are discussed including the combined use of diffraction with electron microscopy and physisorption. The small-angle scattering curve analysis, which is also an important methodology in the field, is out of the scope of this review.