A 5 M 2 X 11 and A 3 M 2 X 9 families (A = monovalent organic cation; M = trivalent metal; X = halogen) are receiving increasing attention because of their combination of easy solution processability and superior ferroelectricity properties. However, synthesizing highly efficient A 5 M 2 X 11 and A 3 M 2 X 9 -type fluorophores with multiple monomeric inorganic units and achieving their structural interconversion remains challenging. Here, we report two novel zero-dimensional (0D) antimony halides, (C 10 H 16 N) 5 Sb 2 Cl 11 •C 2 H 3 N (1) and (C 10 H 16 N) 3 Sb 2 Cl 9 (2), which not only contain two distinct [SbX n ] 3−n units but also have excellent orange (590 nm) and yellow-green emission (540 nm) with high PLQY of 17.7% and 31.5%, respectively. Interestingly, a reversible structural conversion could be triggered by acetonitrile steam stimulation, accompanied by luminescence switching properties. This work not only enriches the structure of hybrid Sb-based halides but also provides the possibility of well-known A 5 M 2 X 11 and A 3 M 2 X 9 families as structural transformation materials.