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Improved scintillation yield and energy resolution as well as afterglow decrease have been recently demonstrated to result from the appropriate choice of Lu/Gd ratio in LGSO:Ce crystals. Observed tendency was attributed to the constrained separation between electrons and holes in solid solutions due to inhomogeneous distribution of cations. Here the effect was further investigated by detailed study of energy relaxation in LGSO:Ce crystals by VUV spectroscopy including temperature dependent time-resolved measurements of luminescence excitation and emission spectra and luminescence kinetics in the excitation energy range 4 to 25 eV at the SUPERLUMI station of HASYLAB, DESY.