X-ray diffraction is sensitive to thin films of atomic dimensions to thicknesses of many tens of microns, by virtue of the x-ray wavelengths employed and the very high diffractionspace resolutions attainable. X-ray methods are generally non-destructive, in that sample preparation is not required, and they can provide a very appropriate route to obtain structural information on thin films and multilayers. Analysis can be performed across the whole spectrum of material types from perfect single crystals to amorphous materials. The choice of the x-ray diffraction analysis procedure depends on the quality of the structural form and therefore this review has been organized to reflect this. Following a description of the various material types, some typically important material parameters have been given arising from the application areas. These material parameters relating to the structure are then categorized into macroscopic and microscopic properties which can then be further subdivided and correlated to the most appropriate analysis method. It is clear from this that x-ray analysis covers the whole range and from this the recent developments will become clear. It is intended therefore that the reader is not compelled to read from beginning to end, but rather be able to find the structural parameter of interest to him/her in a simple way and from that discover the various approaches to its determination.