Recently, many lead‐free metal halides with diverse structures and highly efficient emission have been reported. However, their poor stability and single‐mode emission color severely limit their applications. Herein, three homologous Sb3+‐doped zero‐dimensional (0D) air‐stable Sn(IV)‐based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl4 lattice, which brings different optical properties. Under photoexcitation, (C25H22P)SnCl5@Sb·CH4O (Sb3+−1) does not emit light, (C25H22P)2SnCl6@Sb‐α (Sb3+−2α) shines bright yellow emission with a photoluminescence quantum yield (PLQY) of 92%, and (C25H22P)2SnCl6@Sb‐β (Sb3+−2β) exhibits intense red emission with a PLQY of 78%. The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions. Particularly, Sb3+−1 can be successfully converted into Sb3+−2α under the treatment of C25H22PCl solution, accompanied by a transition from nonemission to efficient yellow emission, serving as a “turn‐on” photoluminescence (PL) switching. Parallelly, a reversible structure conversion between Sb3+−2α and Sb3+−2β was witnessed after dichloromethane or volatilization treatment, accompanied by yellow and red emission switching. Thereby, a triple‐mode tunable PL switching of off–onI–onII can be constructed in Sb3+‐doped Sn(IV)‐based compounds. Finally, we demonstrated the as‐synthesized compounds in fluorescent anticounterfeiting, information encryption, and optical logic gates.