Abstract The development of complementary imaging techniques at beamline I18 at Diamond Light Source (Didcot, UK) to investigate the microstructure of inorganic materials is described. In particular, the use of X-ray micro-imaging techniques to understand the effect of alpha radiation on phyllosilicates, and the nature of individual catalytic particles are reported. Micro X-ray diffraction (µXRD) studies of the former materials have shown structural changes that will affect their adsorption properties, while the chemistry of the catalyst particles has been investigated using micro X-ray fluorescence, µXRD and µX-ray absorption near-edge structure mapping. The distribution of a Mopromoted Pt nitrobenzene hydrogenation catalyst has shown that some of the Pt penetrated to the core of the particle and has the same chemistry as the bulk of the Pt located on the outside of the particle. The phase distribution in an as-prepared Re-Ti-promoted Co Fischer-Tropsch catalyst is reported.