Abstract X‐ray imaging technology has been widely used in the fields of environmental monitoring, safety inspection, nondestructive examination, space exploration, and medical diagnosis, among which scintillation materials play a vital role in indirectly converting X‐ray to visible photons. Here, a zero‐dimensional organic–inorganic hybrid halide C 50 H 44 P 2 SbCl 5 crystal is prepared via a facile antisolvent precipitation method at room temperature. The single crystal of C 50 H 44 P 2 SbCl 5 displays a strong yellow broadband emission centered at 592 nm with a near‐unity photoluminescence quantum yield of 98.42%. Importantly, C 50 H 44 P 2 SbCl 5 crystals show great environmental stability and irradiation stability. Radioluminescence characterization indicates that C 50 H 44 P 2 SbCl 5 crystals exhibit a good linear response to X‐ray dose rates along with an excellent light yield of 44 460 photons MeV −1 , surpassing that of commercial inorganic LuAG:Ce scintillator. The spatial resolution of the C 50 H 44 P 2 SbCl 5 ‐based scintillating screen is determined to be 8.2 lp mm −1 . In conjunction with polymer thin film, the excellent scintillating feature of organic–inorganic hybrid halides offers exciting opportunities for achieving high‐quality flexible X‐ray imaging.