The small size and large trap density have seriously hindered the application of cesium copper iodine single crystals (SCs). Herein, we propose a strategy for synthesizing high-quality and large-sized CsCu2I3 SCs by gradient crystallization. The as-synthesized CsCu2I3 SCs exhibit a large length of 1.7 cm with a low trap density of 4.17 × 109 cm−3. Moreover, such CsCu2I3 SCs show excellent photoelectric response to ultraviolet (UV) irradiation, owing to their high absorption coefficient, large Stokes shift, and one-dimensional electronic structure. The measured responsivity and detectivity of the CsCu2I3 SC-based photodetectors reach the maxima of 24.58 A/W and 1.02 × 1013 Jones, respectively, under 365 nm light irradiation. Due to the outstanding UV detection performance, such photodetectors are also utilized for achieving direct UV imaging with high resolutions.