Recent years have seen a considerable development in the availability of single-crystal diffraction facilities with synchrotron radiation for use in non-biological crystallography, with access to several suitable beam-lines around the world. These can markedly extend the range of materials for which a full crystal structure can be determined, particularly in terms of micro-crystalline samples. Special features of synchrotron radiation such as X-ray wavelength tunability can be exploited. This article explains some of the important relevant properties of synchrotron radiation, demonstrates the importance of these facilities for chemists interested in structural characterisation, and provides examples of results from areas of topical concern, including microporous materials, pharmaceuticals, and supramolecular chemistry.