The isolated [PbBr 6 ] octahedra in the zero-dimensional (0-D) perovskite Cs 4 PbBr 6 crystal lattice trigger localized optical transitions, which exhibits extremely unique optical properties and brings controversial topics concerning its optical properties, particularly about its photoluminescence (PL) nature. Herein, we successfully grown a series of large-scale Cs 4 PbBr 6−m X m (X = Cl, I) single crystals (SCs) from Cs-rich solutions, partially replacing Br with Cl and I, taking advantage of superiorities from SCs to explore optical behavior and eliminate the mutual transformation distraction between Cs 4 PbBr 6 and CsPbBr 3 . No CsPbBr 3 is detected in our Cs 4 PbBr 6−m X m (X = Cl, I) large SCs, whereas they exhibit obvious PL phenomena. It is revealed that the Cs 4 PbBr 6 SC exhibits intense PL, and the replacements of Br with Cl and I can regularly alter the crystal lattice, optical absorption cutoffs, and PL positions and bring multiple PL peaks, among which one is attributed to the Br vacancy (V Br ) and another originates from crystal lattice distortions triggered by both halogen replacements. Therefore, we proposed that the PL nature of CsPbBr 3−m X m (X = Cl, I) SCs originates from crystal lattice distortions that can be induced by both halogen replacements and V Br . Severe local lattice distortion, for example, in Cs 4 PbBr 6 films and powders, definitely can induce Cs 4 PbBr 6−m X m to transform toward CsPbBr 3 and therefore enhance the PL yield.