The luminescence properties of the bismuth compounds Bi 2Ge 3O 9, Bi 12MO 20 ( M = Ge, Ti), and Bi 2Al 4O 9 and of the lead compounds PbGe 3O 7 and PbM 2O 4 ( M = Al, Ga) are reported and discussed. Bi 12MO 20 and probably PbGe 3O 7 show semiconductor-type luminescence. For Bi 12MO 20 blue and red emission bands are reported which both are ascribed to radiative recombination at (deep) defect centre levels in the band gap. The blue emission originates probably from surface defects. The other compounds show broad emission and excitation bands with large Stokes shifts. The transitions occur on one and the same Bi 3+(Pb 2+) ion. From decay time measurements it is found that the energy difference between the two lowest excited levels is very small for all compounds. The large Stokes shifts and small trap depths are discussed in terms of the asymmetrical coordination of the 6 s2 ions in the compounds under discussion. It is concluded that asymmetrically surrounded Bi 3+ ions give rise to luminescence which is characterized by a broad emission band which shows a very large Stokes shift (⋍2 eV).