In the field of photonics, alkali copper(I) halides attract considerable attention as lead-free emitters. The intrinsic quantum confinement effects originating from low-dimensional electronic structure lead to high photoluminescence quantum yields (PLQYs). Among them, Cs(3)Cu(2)I(5)is the most promising candidate, satisfying both high PLQY and air stability. In this study, a strategy to explore a new material meeting these requirements through the use of the mixed-anions of I(-)and Cl(-)is proposed. The expectation is maintained that the large difference in ionic radii between them likely results in the formation of a novel compound. Consequently, Cs(5)Cu(3)Cl(6)I(2)with a 1D zigzag chain structure is discovered. This material exhibits blue emission (approximate to 462 nm) with a near-unity quantum yield of 95%. An electronic structure calculation reveals that the localized nature of the valence band maximum is crucial in obtaining efficient self-trapped exciton emission. Moreover, the iodine-bridged 1D connectivity significantly enhances the chemical stability of Cs5Cu3Cl6I2, compared with the pure chloride phase. The present findings provide a new perspective for developing air-stable alkali copper(I) halides with highly efficient luminescence.