Ternary copper halides have become promising materials for UV photodetection due to their stability and eco-friendliness. However, the uncontrollable crystallization induces high-concentration defects in these films, inherently limiting further improvement in device performance. Herein, we reveal the antisolvent-assisted crystallization kinetics mechanism of CsCu2I3 during the film-forming process. The nucleation rate is manipulated by adjusting precursor supersaturation using different antisolvents, resulting in decreased density and preferential orientation of the nuclei within the wet film. Subsequent annealing leads to a homogeneous and low-defect CsCu2I3 film with 40-μm-scale spherulites. A resulting visible-blind ultraviolet photodetector exhibits a responsivity of 8.73 A W-1, a specific detectivity of 5.28 × 1012 jones, and a response speed of 1.12 ms. The unencapsulated photodetector shows negligible degradation of responsivity in ambient air (∼70% humidity) for one month. Moreover, the flexible device with a responsivity of 420.2 mA W-1 and a detectivity of 1.18 × 1012 jones also shows excellent bending stability.