Various experiments show that low‐energy electron‐induced X‐ray spectrometry (LEEIXS), using a gas discharge tube as an efficient and stable electronic excitation source, represents a powerful new technique in many fields of research related to surface and near‐surface chemical characterization of materials. The instrument is a wavelength‐dispersive X‐ray spectrometer capable of high qualitative or quantitative performances in the soft and ultra‐soft region (λ = 0.3—10 nm). LEEIXS applications given in this paper demonstrate how chemical, electrochemical or physical treatments of various substrates modify the solid surface composition.