SummaryWe describe a cathodoluminescence spectrometer that is attached to an analytical transmission electron microscope. After a brief consideration of the set‐up and the peculiarities of recording spectra and of mapping defect distributions in panchromatic and monochromatic cathodoluminescence, we discuss two examples of applications. Emphasis is placed on the potential for obtaining novel information about materials and processes on a microscopic and a nanoscopic scale by combining cathodoluminescence with the structural and chemical information for the same site of the specimen. We select an example concerning the role of In distribution in light emission from InGa/GaN quantum wells and a second one concerning the analysis of the initial electron radiation damage of Cu(In,Ga)Se2 photovoltaic films.