In this work, the crystal structure and electronic structure as well as the synchrotron radiation vacuum ultraviolet-ultraviolet-visible (VUV-UV-vis) luminescence properties of Li 6 Y(BO 3 ) 3 (LYBO):Ce 3+ phosphors were investigated in detail. The Rietveld refinement and DFT calculation reveal the P2 1 /c monoclinic crystal phase and the direct band gap of the LYBO compound, respectively. Only one kind of Ce 3+ 4f-5d transition is resolved in terms of the low temperature VUV-UV excitation, UV-vis emission spectra and luminescence decay curves. Furthermore, by constructing the vacuum referred binding energy (VRBE) scheme and applying the frequency-degenerate vibrational model, the impacts of 5d electron binding energy and electron-phonon coupling on luminescence of Ce 3+ in LYBO are analysed. The results show that the Ce 3+ emission in LYBO possesses a moderate intrinsic thermal stability. With the increase in concentration, the thermal stability of the emission gets worse due to the possible thermally-activated concentration quenching. In addition, the simulation of Ce 3+ emission profile at low temperature reveals that the 4f-5d electronic transitions of Ce 3+ ions can be treated to couple with one frequency-degenerate vibrational mode having the effective phonon energy of ∼257 cm −1 with the corresponding Huang-Rhys parameter of ∼6, which indicates a strong electron-phonon interaction of Ce 3+ luminescence in the Li 6 Y(BO 3 ) 3 host. Finally, the X-ray excited luminescence spectrum of the LYBO:5%Ce 3+ phosphor is measured to check the potential scintillator applications.