Spatially separated stable charge centers -self-trapped holes, trapped electrons, dopant ionic centers and radicals were generated in an Ar matrix doped with Xe and N 2 by a low energy electron beam. A combination of the cathodoluminescence (CL) with the photon-stimulated luminescence (PSL) and photonstimulated exoelectron emission (PSEE) methods was used to monitor center formation and selected relaxation channels -charge recombination reactions and exoelectron emission. PSEE from pre-irradiated Ar samples was registered simultaneously with N line emission. Vacuum ultraviolet (VUV) intrinsic and extrinsic recombination luminescence from pre-irradiated samples has been detected to confirm the suggested relaxation path of the stored energy. An afterglow of the N line can be considered as an internal source of photons which releases electrons from the traps and being a triggering mechanism of relaxation processes: (i) -exoelectron emission, (ii) -radiative recombination of charge species. 1 Introduction An exposure of solid insulators to ionizing radiation results in generation of metastable centers such as self-trapped/trapped charge carriers and structural defects. Spatially separated charge carriers remain stable at low temperatures after completing irradiation. Relaxation processes can be stimulated by heating or by photon flux. In our study we focused on the photon-stimulated relaxation.Methods of activation spectroscopy are especially powerful tools for the investigation of a relaxation in solids and the method of thermally stimulated luminescence (TSL) is the most common in use [1][2][3][4][5][6][7]. Recent experiments revealed thermally stimulated exoelectron emission (TSEE) from solid Ne [8] and Ar [9,10]. The latter studies showed a correlation in the yields of exoelectrons and VUV photons of the intrinsic recombination emission from pre-irradiated solid Ar. It was suggested [11] and then demonstrated [5,6,10] that thermally stimulated recombination of neutral guest O atoms in Ar matrix followed by O 2 * formation at 23 K and radiative decay of O 2 results in the emission of exoelectrons from solid Ar. It posed the question on the influence of visible light on the relaxation path in rare-gas solids (RGS).Relaxation processes in RGS are still not clearly understood. There are only a few publications dedicated to PSEE [5,10,12] and to the intrinsic VUV recombination luminescence caused by an external photon source [13].We present new results -relaxation channels involving photon-stimulated radiative recombination (intrinsic and extrinsic) of charge centers with electrons in VUV range and corresponding PSEE.