The article presents the results of measuring the luminescence spectra and luminescence excitation spectra for YAG:Eu with europium concentrations of 2, 6, 8, and 10%. The materials were synthesized by solid-phase synthesis. For samples with europium concentrations of 2, 8, and 10%, the diffraction patterns showed full agreement with the phases. However, the yttrium–aluminum–perovskite phase was present in the sample with a concentration of 6%, even though the samples were obtained under the same conditions. The spectra of the photoluminescence excitation and photoluminescence were recorded for all samples. The concentration dependences of the luminescence bands and luminescence excitation bands were also plotted. The bandgap and absorption spectra were simulated for the sample of YAG:Eu, doped with 2–4 ions of europium for comparison.