The process of excitations of the glutamine molecules in the gas phase during collisions with low-energy electrons (0–70 eV) for samples before and after irradiation (11.5 MeV) at the M-30 microtron with doses of 10 kGy have been investigated by the optical spectroscopy method. Optical spectra were studied in the wavelength range 200–520 nm; the effects caused by both external radiation and the scanning electron beam with the 30, 50, and 70 eV energy were investigated. For the most intense emission of the molecular fragments, their thresholds and excitations’ energy dependences were determined in the range of electron energies up to 30 eV. The new effect has been established: for λ > 310 nm, the irradiated samples’ emission increased both by increasing the scanning beam’s electron energy and the emitted light wavelength. However, for values of λ < 310 nm, there is an opposite dependence. The simulation of the glutamine transformations under irradiation was carried out within the method of structural combinations, which allows determining all sets of molecular structures of glutamine without and in the presence of ‘broken’ chemical bonds. The role of radiation in the formation of metastable molecular structures, which determine the features of the optical and mass spectra of irradiated glutamine samples, is investigated.