Copper‐based organic–inorganic hybrid halides (OIHHs) have garnered significant interest in X‐ray imaging due to their flexible structural adjustability, efficient light emission, strong X‐ray absorption, etc. Herein, four copper‐based OIHH crystals composed of the same organic ligands (isopropyl triphenylphosphonium cations, IPP+) and inorganic parts (Cu2I42−) are synthesized by varying the ratios of raw materials and types of reaction solvents. Although these crystals share identical structures, they exhibit different luminescent behaviors (blue, green, white, and yellow) attributed to vacancy defects originating from CuI. Notably, the novel copper‐based OIHH (CP2) with green emission shows the best luminescence efficiency (99.54%) and excellent scintillation performance (50675 photons MeV−1). The traditional technology of scintillation screens mixing scintillator powders and polymers often results in light scattering due to powder aggregation and inhomogeneity. To address this challenge, the dispersant polyvinyl pyrrolidone is introduced to prepare uniform rod‐like microcrystals of CP2. The scintillation screen based on CP2 microcrystals achieves a high spatial resolution of 16–18 lp mm−1, surpassing the resolution of most copper‐based OIHH scintillators. Furthermore, it is imaging capabilities are validated using a commercial X‐ray flat panel detector, demonstrating imaging performance comparable to that of commercial scintillators.