AbstractFor over the past two decades it has been believed that the intense orange-red photoluminescence in Bismuth-doped materials originates from Bi$$^{2+}$$
2
+
ions. Based on the results from magnetic circular polarization experiments, we demonstrate that this hypothesis fails for Bismuth-doped silica glasses. Our findings contradict the generally accepted statement that the orange-red luminescence arises from $$^{2}P_{3/2}(1)$$
2
P
3
/
2
(
1
)
$$\rightarrow$$
→
$$^{2}P_{1/2}$$
2
P
1
/
2
transition in a divalent Bismuth ion. The degree of magnetic circular polarization of this luminescence exhibits non-monotonic temperature and field dependencies, as well as sign reversal. This complex behaviour cannot be explained under the assumption of a single Bi$$^{2+}$$
2
+
ion. The detailed analysis enables us to construct a consistent diagram of energy levels involved in the magneto-optical experiments and propose a new interpretation of the nature of orange-red luminescence in Bismuth-doped silica glass. A centre responsible for this notorious photoluminescence must be an even-electron system with an integer total spin, presumably a dimer of Bismuth ions or a complex consisting of Bi$$^{2+}$$
2
+
and an oxygen vacancy.