The large penetration power of high-energy X-rays (>60 keV) raises interesting prospects for new types of structural characterizations of polycrystalline materials. It becomes possible in a non-destructive manner to perform local studies, within the bulk of the material, of the fundamental materials physics properties: grain orientations, strain, dislocation densities etc. In favourable cases these properties may be mapped in three dimensions with a spatial resolution that matches the dimensions of the individual grains. Imbedded volumes and interfaces become accessible. Moreover, the high energies allow better in-situ studies of samples in complicated environments (industrial process optimization). General techniques for research in this energy range have been developed using broad-band angle-dispersive methods, on-line two-dimensional detectors and conical slits. Characterizations have been made at the level of the individual grains and grain boundaries as well as on ensembles of grains. The spatial resolution is presently of the order of 10-100 micom. Four examples of applications are presented along with an outlook.