Copper-based lead-free perovskite derivatives have recently drawn great attention for their excellent optoelectronic properties and potential applications in light-emitting diodes (LEDs) and photodetectors. Herein, facile synthesis methods of cooling crystallization and wet ball milling (WBM) are adopted to synthesize K2CuCl3, resulting in single crystals (SCs) and powder samples, respectively. The as-fabricated K2CuCl3 samples exhibit blue–violet emission, with the highest photoluminescence quantum yield (PL QY) of 70% (under 280 nm excitation), and the photoluminescence (PL) is attributed to the self-trap excitons (STEs) emission. We also test the scintillation properties of K2CuCl3 for X-ray detection and imaging applications. A down-conversion LED is finally made by using K2CuCl3 as phosphor. As-synthesized K2CuCl3 can be used for either photoluminescence under UV light or X-ray imaging under X-ray radiation. -- Present in ms [ABSTRACT FROM AUTHOR]