The physical properties of multilayer films depend critically on both the microstructure and the chemical profile across the layers, often at a scale close to atomic, because of the small thickness of the layers. This paper describe some of the techniques used to characterise metallic multilayer films, and gives illustrations of the type of data which can be obtained for each technique. The techniques include high-resolution electron microscopy, electron diffraction, X-ray diffraction, atom probe microanalysis and X-ray and electron energy loss spectroscopies using a scanning transmission electron microscope.