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Ce:Li 6 Y(BO 3) 3 (LYBO) is a promising thermal neutron scintillator that can be grown into bulk single crystals by the Czochralski method although it melts incongruently. This study achieves 1-inch Ce:LYBO, and demonstrates the collateral flux-growth of LiY 6 O 5 (BO 3) 3 (LYOB) single crystals at the bottom of the crucible during the pulling of LYBO from a stoichiometric melt. Both LYBO and LYOB belong to monoclinic crystal system with the same space group. Thermal analysis shows that LYOB itself is more incongruent than LYBO, decomposing mainly into Y 16.86 B 8 O 38 phase when heated up to 1500 ​°C. In contrast to the typical bluish emission of Ce-doped scintillators, like the case of Ce:LYBO, Ce:LYOB crystals exhibit a broad emission peaking in the orange wavelength region, as a result from an extraordinarily large Stokes shift. The ultrafast photoluminescence (PL) decay of Ce:LYOB is due to dominant non-radiative processes that also cause obvious luminescence quenching. This study reports for the first time high-quality Ce:LYOB single crystals, which are characterized in terms of single crystal diffraction, thermal analysis, optical transmittance, excitation and PL at room temperature, PL decay and Raman spectroscopy. Simultaneous crystal growth of 1-inch Ce:Li 6 Y(BO 3) 3 and millimeter high-quality Ce:LiY 6 O 5 (BO 3) 3 , and investigations on their structure, thermal analysis and optical properties. [Display omitted] • 1-inch Ce:Li 6 Y(BO 3) 3 crystal that is transparent and cracks/inclusion-free. • Flux-growth of high-quality Ce:LiY 6 O 5 (BO 3) 3 single crystals. • Thermal and optical properties of Ce:LiY 6 O 5 (BO 3) 3 were reported for the first time. • Ce:LiY 6 O 5 (BO 3) 3 emits an orange-reddish light originating from large Stokes shift. [ABSTRACT FROM AUTHOR]