The abrupt reorganization of the electronic configuration of spin‐crossover (SCO) compounds upon the transition from the low‐spin (LS) to the high‐spin (HS) state leads to significant changes in their structural, optical, and magnetic properties. As spin‐transitions can be triggered by a variety of external stimuli such as variations in temperature, pressure, or through light irradiation, these systems have attracted considerable attention for the design of multifunctional and stimuli‐responsive molecular materials. In this context, the synergistic coupling of SCO and luminescent properties holds great promise for the development of molecular spintronic devices capable of correlating the luminescence with an external perturbation, or of probing the magnetic state of the metal center through variations in emission intensity. This contribution provides a comprehensive overview of the field of luminescent SCO materials, with particular emphasis on systems that exhibit a genuine interplay between the two properties, both in materials and at the molecular level.