In the last ten years, the scanning transmission electron microscope (STEM) has become capable of forming electron probes of atomic dimensions making possible a new approach to high-resolution electron microscopy, Z-contrast imaging. Formed by mapping the intensity of high-angle scattered electrons as the probe is scanned across the specimen, the Z-contrast image represents a direct map of the specimen scattering power at atomic resolution. It is an incoherent image, and can be directly interpreted in terms of atomic columns. High angle scattering comes predominantly from the atomic nuclei, so the scattering cross section depends on atomic number (Z) squared. Z-contrast microscopy can therefore be used to study compositional ordering and segregation at the atomic scale. Here we present three examples of ordering: first, ferroelectric materials, second, III-V semiconductor alloys, and finally, cooperative segregation at a semiconductor grain boundary, where a combination of Z-contrast imaging with first principles theory provides a complete atomic-scale view of the sites and configurations of the segregant atoms.