Ce3+ and Eu2+ doped and Ce3+-Eu2+ co-doped Sr2MgSi2O7 phosphors are prepared via a high-temperature solid-state reaction technique. The synchrotron radiation vacuum ultraviolet-ultraviolet (VUV-UV) excitation and ultraviolet-visible (UV-vis) emission spectra of diluted Ce3+ and Eu2+ doped Sr2MgSi2O7 samples are measured at cryogenic temperatures. The electron-vibrational interaction (EVI) between Ce3+ and its surroundings is analyzed. The dependencies of the 4f-5d transitions of Ce3+ on the structure of the host compounds Sr2MgSi2O7, Ba2MgSi2O7 and BaMg2Si2O7 are discussed in detail. Then the thermal quenching channel is proposed based on the measurements of temperature dependent luminescence intensities and decay times of Ce3+ and Eu2+ in Sr2MgSi2O7, and the Ce3+ → Eu2+ energy transfer mechanism is understood by three luminescence dynamic models. In addition, Sr2MgSi2O7:Ce3+/Eu2+ samples are evaluated for the possibilities of X-ray detection applications using X-ray excited luminescence (XEL) spectroscopy, and it was found that they are not suitable.@en