Luminescent aggregates of the type of Cs4PbBr6 dispersed in a CsBr crystal lattice have been observed for the first time in as‐grown and in annealed (at 160 to 260 °C for 20 h) CsBr:Pb single crystals with a sufficiently large lead concentration (0.3 to 1.8 mol% in the melt). Absorption spectra as well as spectral, polarization and kinetic characteristics of their luminescence peaking near 3.3 eV and excited near 4.0 eV and 5.2 to 5.1 eV have been studied at 4.2 to 200 K. The characteristics of the Cs4PbBr6 aggregates have been compared with those of a Cs4PbBr6 single crystal and with the characteristics of Pb2+ centres in a quenched CsBr:Pb crystal. The origin and the structure of the corresponding relaxed excited states have been discussed.