With the rapid development of silicon-based light detectors with high detection efficiency and long-wavelength sensitivity, the development of near-infrared scintillation crystals has become a hotspot. Especially, the Sm2+ doped europium-based halide crystals exhibit excellent near-infrared luminescence properties. In this paper, Cs4EuI6∶Sm near-infrared scintillation crystals with a size of cm-level were successfully prepared by Bridgman method. The composition and structure were discussed by XRD, XPS and ICP-OES methods, indicating that the Sm2+ was introduced and has no obvious effect on the crystal structure of the matrix. Under ultraviolet and X-ray excitation, the crystal has two luminescence centers (Eu2+ and Sm2+), and the emission peaks are located at 450 and 840 nm, respectively, corresponding to the 5d→4f luminescence of Eu2+ and Sm2+. The decay time of Eu2+ and Sm2+ is at the level of microsecond under ultraviolet excitation. The results show that the emission wavelength gradually varies from blue to near infrared as Sm2+ doping concentration increased. The effects of Sm2+ concentration on the luminescence properties, Eu2+-Sm2+ energy transfer and decay time of the crystals were also studied, which means that the luminescence properties can be tuned by adjusting the Sm2+ doping concenstration.