Time-resolved luminescence spectroscopy has been widely used in studies of electronic excitations and their dynamics in insulators. Present paper discusses the potential of vacuum ultraviolet spectroscopy applied for wide band gap crystals using classical synchrotron radiation as well as more recently developed pulsed femtosecond short-wavelength light sources. Optical spectroscopy using novel free electron lasers and laser systems based on higher harmonic generation process allow detailed investigation of the interaction between electronic excitations and behaviour of solids under extreme radiation conditions. Significant changes in the quantum yield and emission decay kinetics as well as surface damage of single crystals were observed for CdWO 4 and CaWO 4 crystals studied in the temperature range of 8-300 K. However, in the range of excitation densities applied, up to~10 12 W/cm 2 , the nature of luminescence centres and their characteristic emission spectra remained similar to those observed at low excitation densities. Time-resolved luminescence spectroscopy has been widely used in studies of electronic excitations and their dynamics in insulators. Present paper discusses the potential of vacuum ultraviolet spectroscopy applied for wide band gap crystals using classical synchrotron radiation as well as more recently developed pulsed femtosecond short-wavelength light sources. Optical spectroscopy using novel free electron lasers and laser systems based on higher harmonic generation process allow detailed investigation of the interaction between electronic excitations and behaviour of solids under extreme radiation conditions. Significant changes in the quantum yield and emission decay kinetics as well as surface damage of single crystals were observed for CdWO 4 and CaWO 4 crystals studied in the temperature range of 8-300 K. However, in the range of excitation densities applied, up to ~10 12 W/cm 2 , the nature of luminescence centres and their characteristic emission spectra remained similar to those observed at low excitation densities. 1 Introduction Storage rings (synchrotrons) are well-established short-wavelength light sources, which are widely exploited for various spectroscopic techniques characterising structural properties as well as electronic excitations of various materials. Synchrotron radiation (SR) has played an important role in the development of luminescence spectroscopy and in the investigation of dynamical processes as reviewed recently by Zimmerer [1]. As a tuneable source, along with its inherent time resolution and high repetition rate (a few MHz) SR allows revealing complicated relaxation processes induced by vacuum ultraviolet (VUV) photons in wide gap materials. The pulse duration of SR is typically ~100 ps and the photon fluxes generated reach ~10 12 photons per second. These are sufficient for spectroscopic purposes, but not for direct observation of effects due to high density of electronic excitations reported for the irradiation by ion beams [2] or by pulsed nanosecond elect...