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Luminescence and scintillation characteristics of four selected material systems, namely CsI : Tl(Na), CeF₃, PbWO₄ and Ce‐doped aluminium perovskites XAlO₃ : Ce (X=Y, Lu, Y–Lu) are reviewed. The progress in their physical understanding and related optimisation of their characteristics and technology are demonstrated. The important role of various defect states in the scintillator performance of these materials is stressed, which has led to the need for a deeper study of the processes of energy transfer and storage to achieve their intrinsic limits and full exploitation in scintillation detectors.