The luminescence properties of Tb3+ in Tb3+−Tb3+ and Tb3+−Gd3+ majority-type pairs in CsCdBr3 are investigated at 77 K and room temperature. 5D3→5D4 cross-relaxation rates for Tb3+ in Tb3+−Tb3+ pairs are determined. The intrinsic 5D3→5D4 and 5D3→7FJ relaxation rates of Tb3+ in the majority-pair site are estimated. The relative numbers of Tb3+−Tb3+ and Tb3+−Gd3+ pairs in Tb/Gd-doped CsCdBr3 are shown to be consistent with statistical pair formation.

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