A novel NIR emitting scintillator with 825 nm was developed by doping Sm2+ in Cs4Eu(Br,I)6 crystal. The single crystals of Cs4Eu(Br,I)6:Sm were successfully grown by the Bridgman method. The crystal structure and valence state was approved by XRD and XPS methods. The luminescence properties and energy transfer were systematically investigated. The energy transfer mechanism is variable for different Sm2+ concentration. The PL decay profiles show that the Sm2+-related emission has fast decay of nanosecond. The proportion of fast decay can be tunable by adjusting Sm2+ doped concentration. The Sm2+ doped europium -host material will have a potential application for unclear detection as near-infrared (NIR) scintillators.