This Progress Report discusses the chemical sensitivity of Kβ valence to core X‐ray emission spectroscopy (vtc‐XES) and its applications for investigating 3d‐transition‐metal based materials. Vtc‐XES can be used for ligand identification and for the characterization of the valence electronic levels. The technique provides information that is similar to valence band photoemission spectroscopy but the sample environment can be chosen freely and thus allows measurements in presence of gases and liquids and it can be applied for measurements under in situ/operando or extreme conditions. The theoretical basis of the technique is presented using a one‐electron approach and the vtc‐XES spectral features are interpreted using ground state density functional theory calculations. Some recent results obtained by vtc‐XES in various scientific fields are discussed to demonstrate the potential and future applications of this technique. Resonant X‐ray emission spectroscopy is briefly introduced with some applications for the study of 3d and 5d‐transition‐metal based systems.