The luminescence properties of the bismuth compounds BizGe309, BiuMOrO (M = Ge, Ti), and Bi2A1409 and of the lead compounds PbGe,O, and PbM204 (M = Al, Ga) are reported and discussed. BilZMOZO and probably PbGe307 show semiconductor-type luminescence. For Bi&fOr,, 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 B?+(Pb*+) 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 6sz ions in the compounds under discussion. It is concluded that asymmetrically surrounded Bi3+ ions give rise to luminescence which is characterized by a broad emission band which shows a very large Stokes shift (22 eV).