X-ray diffraction (XRD) is a useful, complementary tool in the structural characterization of porous silicon (pSi), providing information not readily available from direct visualization techniques such as electron microscopies. This review outlines key considerations in the use of diffraction techniques for analyses of this material in both thin film form and freestanding porous Si nano or microparticles. Examples of the range of content in the analysis of pSi are provided, including formation mechanisms, layer thickness, extent of pSi oxidation, and degree of crystallinity. Such properties influence practical properties of pSi such as its biodegradability. We also focus on selected key properties where XRD has been particularly informative:(a) strain,(b) the structural analysis of pSi multilayers, and (c) an analysis of pSi loaded with small molecules of fundamental or therapeutic interest.