Abstract Low‐dimensional copper‐based halide single crystals are considered excellent scintillators for indirect X‐ray detection, but their potential in direct X‐ray detection has not been investigated. Herein, high‐quality pure Cs 3 Cu 2 I 5 and Li‐doped Cs 3 Cu 2 I 5 :Li single crystals are grown by the Bridgman method. The Li + dopant enhances the photoelectric properties of the Cs 3 Cu 2 I 5 single crystal by extending the carrier lifetime, improving the carrier mobility from 6.49 to 9.52 cm 2 V −1 s −1 , and increasing the mobility‐lifetime (µ τ ) product from 1.4 × 10 −4 to 2.9 × 10 −4 cm 2 V −1 . The sensitive direct X‐ray detector with a vertical device configuration of Au/Cs 3 Cu 2 I 5 :Li single crystal/PCBM/Au is fabricated and demonstrated to have a high sensitivity of 831.1 µC Gy air −1 cm −2 and low detection limit of 34.8 nGy air s −1 . Furthermore, the detector shows negligible baseline current drift and excellent stability upon X‐ray radiation.