The thermal quenching of Eu2+ 5d–4f emission on Ba, Sr, or Ca sites in compounds is often attributed to a large displacement between the ground state and excited state in the configuration coordinate diagram. This work will demonstrate that the ionization of the 5d electron to conduction band states is the genuine quenching mechanism. A model is proposed to explain why in some types of compounds the quenching temperature decreases when going from the Ba variant via the Sr variant to the Ca variant and in other types of compounds the reverse behaviour occurs. The nature of the bottom of the conduction band plays an important role in this.