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This research is directed on creating by liquid phase epitaxy the single crystalline film scintillators based on undoped and Bi doped CdWO4 compounds as well as the phoswich detector based on “CdWO4:Bi or CdWO4 films/CdWO4 or CdWO4:Bi crystals” epitaxial structures. The luminescent and scintillation properties of the undoped and Bi3+ doped (in a concentration range of 0.04-0.25 at. %) CdWO4 films, grown by LPE method from Na2WO4 flux, were compared with the properties of CdWO4 bulk crystal analogs, grown from melts by the Czochralski method. Using the traditional luminescence spectroscopy and the luminescence spectroscopy under excitation by pulsed synchrotron radiation with energy in the fundamental absorption range of CdWO4 host, we have also examined the nature of different emission centers and studied energy transfer processes from tungstate hosts to Bi3+ ions and defect centers in CdWO4 and CdWO4:Bi films and their crystal analogs.