The electron probe micoranalyzer, which was initially introduced by Castaing, has proven to be a versatile and important instrument in the fields of ceramics, metallurgy, mineralogy, biology, and solid-state electronics. A review is presented, beginning with the various interaction effects which occur when 5–50 keV electrons impinge on solids. These effects include characteristic and continuum x-ray emission, primary and secondary backscattered electron emission, and production of excess electron-hole pair in semiconductors. The characteristic or line x-ray emission is produced by direct ionization of the target atoms with subsequent radiative decay, and is used for nondestructive qualitative and quantitative analysis with micron spatial resolution. For trace analysis, the limit of detectability is approximately 100 ppm at best. With a typical analysis volume of 1 μm3 and a mass density of 10 g/cm3, this corresponds to a weight sensitivity of approximately 10−15 g. Experimental results are given for the quantitative analysis of sputtered EuO films with thicknesses between 0.3 and 0.5 μm. Scanning electron microscopy can be performed with primary and secondary electrons, as well as x-ray emission. A 200 mesh Cu grid superimposed on a 1000 mesh Ag grid is used as a target to illustrate the use of secondary electron emission intensity for topology micrographs, primary backscattered electron intensity for mass-density micrographs, and characteristic x-ray intensity for elemental micrographs. In addition to composition, the electron probe can be used to determine the thickness of thin films. By increasing the accelerating voltage of the electron beam until penetration to the substrate is accomplished, the thickness of phospho-silicate glass films in the range 700–4000 Å can be determined with an accuracy of ±150 Å. The chemical valence state of atoms can be studied with the long wavelength x-ray spectra. For example, the wavelength position of the peak intensity from Si has been used to reveal the presence of both metallic Si and Si4+ in silicon oxide thin films. In addition, the intensity ratio of two different x-ray lines from the first transition series elements varies with chemical state. Particular attention is devoted to the use of cathodoluminescence for characterizing direct band-gap semiconductors such as GaAs. Band-edge luminescence can be used in a scanning electron microscope mode to display inhomogeneities such as edge dislocations and p-n junctions, as well as bulk dopant inhomogeneities. The voltage dependence of cathodoluminescence can be used to determine transport properties such as minority carrier diffusion length and surface recombination velocity. Transient cathodoluminescence can be used to determine minority carrier lifetime. The quantitative analysis of rare earth materials by cathodoluminescence has also been used to detect trace concentrations. These methods are applicable to epitaxial thin films in general, and to polycrystalline films in some particular cases.