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Among other emissions, the natural cinnabar presents, under cathodic excitation, a broad red band. Examining the spectral properties of the emitted intensity and of the radiative recombination probability between 4.2 and 300 K, an attempt is made to elucidate its mechanism of formation. The analysis of spectral modifications (shape, half‐width, peak energy, intensity) according to the temperature leads to a diagram of transitions between at least two vibro‐electronical states (one excited and one fundamental) of a same centre, the fundamental state being situated at about 300 meV above the valence band. The shape of the spectral distribution of life time is only compatible with the existence of a band at the origin of transitions and a model of centre is suggested possessing an excited band and submitted to an important vibrational coupling of the lattice.

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