X-ray elemental mapping and X-ray spectrum imaging are powerful microanalytical tools. However, their scope is often limited spatially by the raster area of a scanning electron microscope or microprobe. Limited sampling size becomes a significant issue when large area (>10 cm2), heterogeneous materials such as concrete samples or others must be examined. In such specimens, macro-scale structures, inclusions, and concentration gradients are often of interest, yet microbeam methods are insufficient or at least inefficient for analyzing them. Such requirements largely exclude the samples of interest presented in this article from electron probe microanalysis. Micro X-ray fluorescence–X-ray spectrum imaging (μXRF-XSI) provides a solution to the problem of macro-scale X-ray imaging through an X-ray excitation source, which can be used to analyze a variety of large specimens without many of the limitations found in electron-excitation sources. Using a mid-sized beam coupled with an X-ray excitation source has a number of advantages, such as the ability to work at atmospheric pressure and lower limits of detection owing to the absence of electron-induced bremsstrahlung. μXRF-XSI also acts as a complement, where applicable, to electron microbeam X-ray output, highlighting areas of interest for follow-up microanalysis at a finer length scale.