Compositional variations in thin films can introduce lattice-parameter changes and thus create stresses, in addition to the more usual stresses introduced by substrate-film mismatch, differential thermal expansion, etc. Analytical electron microscopy comprising X-ray energy-dispersive spectrometry within a probe-forming field-emission gun scanning transmission electron microscope (STEM) is one of the most powerful methods of composition measurement on the nanometer scale, essential for thin-film analysis. Recently, with the development of improved X-ray collection efficiencies and quantitative computation methods it has proved possible to map out composition variations in thin films with a spatial resolution approaching 1-2 nm. Because the absorption of X-rays is dependent on the film thickness, concurrent composition and film thickness determination is another advantage of X-ray microanalysis, thus correlating thickness and composition variations, either of which may contribute to stresses in the film. Specific phenomena such as segregation to interfaces and boundaries in the film are ideally suited to analysis by X-ray mapping. This approach also permits multiple boundaries to be examined, giving some statistical certainty to the analysis particularly in nano-crystalline materials with grain sizes greater than the film thickness. Boundary segregation is strongly affected by crystallographic misorientation and it is now possible to map out the orientation between many different grains in the (S)TEM.