An overview of recognized structural defects, impurities and related trapping levels and their role in the scintillation mechanism is provided and discussed in single crystal materials belonging to tungstate, Ce‐ or Pr‐doped aluminum perovskite, garnet and finally to Ce‐doped silicate scintillators. New achievements and open problems in deeper understanding of electron and hole self‐trapping phenomena and of the nature of defects in the crystal structure and their ability to localize migrating charge carriers are indicated. Fast optical ceramics and nanocomposite materials are pointed out as possible future advanced scintillators. Such novel technologies can in principle explore materials which are not available in the bulk single crystal form, but their figure‐of‐merit is dramatically dependent on the surface‐interface defect states and related trapping and nonradiative recombination phenomena. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)