Neoteric Mn2+‐activated Cs3Cu2I5 yellow‐emitting halides were achieved by the simple solid‐state reaction route. The near‐ultraviolet light was the suitable excitation lighting source for the resultant halides. The resultant halides exhibited bright yellow emission under the excitation of 378 nm and the optimum dopant content was 11 mol%. The multipole‐multipole interaction contributed to the concentration quenching mechanism and the critical distance was 28.65 Å. The thermal resistance of the prepared compounds was identified by the temperature‐dependent emission spectra. Ultimately, the designed light‐emitting diode showed bright white light with satisfied color rendering index, proper color coordinate, and suitable correlated color temperature. These results indicated that the prepared yellow‐emitting halides were suitable for indoor illumination.