Scintillation materials have been widely used in various fields, such as medical diagnosis and industrial detection. Chalcogenides have the potential to become a new generation of high-performance scintillation materials due to their high effective atomic number and good resistance to radiation damage. However, research on their application in radiation detection is currently very scarce. Herein, single crystals of rare earth ion-doped ternary chalcogenides NaGaS 2 /Eu were grown by a high-temperature solid-phase method. It exhibits unique characteristics of structure transformation by absorbing water molecules from the air. To maintain the anhydrous phase of the material, we have used a strategy of organic−inorganic composites of epoxy resin and NaGaS 2 / Eu to prepare devices for radiation detection and discuss the irradiation luminescence properties of the two phases. The anhydrous phase of NaGaS 2 /Eu demonstrates excellent sensitivity to X-rays, with a low detection limit of 250 nGy s −1 , which is approximately 1/22 of the medical imaging dose. Additionally, composite flexible films were prepared, which exhibited excellent performance in Xray imaging. These films enable clear observation of a wide range of objects with a high spatial resolution of up to 13.2 line pairs per millimeter (lp mm −1 ), indicating that chalcogenide holds promising prospects in the realm of X-ray imaging applications.