Cs2LiLaBr6:Ce (CLLB) crystal has broad applications due to its excellent scintillation properties. So far, there is no consensus on preferred Ce doping concentration of CLLB crystals for optimal scintillation performance. And the segregation behavior of Ce in CLLB is still open for research. Herein, the Ce concentrations along the CLLB ingot was measured. The effects of actual Ce concentration on scintillation properties and neutron/gamma discrimination ability were discussed. The effective segregation coefficient of Ce in CLLB crystals was calculated to be 1.59. The scintillation performance varied with the actual concentration of Ce. The energy resolutions (@662 keV) remained at 3.5% as the actual concentration of Ce exceed 2%. The neutron/gamma discrimination capability increased until the Ce concentration reached 3%. This work contributes to precise the growth and performance optimization of CLLB crystals.