Two hybrid chloroantimonates(III), [Bzmim]₃SbCl₆ (1, Bzmim=1‐benzyl‐3‐methylimidazolium, T_m1=410 K) and [Bzmim]₂SbCl₅ (2, T_m2=348 K) are presented. 1 exhibits green emission (quantum efficiency of 87.5 %); 2 exhibits blue and red emissions under the irradiation of 310 and 396 nm light, respectively. Using different cooling methods, crystalline 1 and IL@2 (IL=ionic liquid of [Bzmim]Cl) could be generated from the molten 1. Reversible structural and PL transformation triggered by moisture or heat was observed between 1 and IL@2. Such PL switching, combined with the crystallization‐induced PL properties of 1 and 2, resulted in the firstly reported triple‐mode reversible PL switching, that is, on–off (T>T_m1), color switching (T<T_m2), and on–off–on (T_m2<T<T_m1). Furthermore, ink‐ and mask‐free laser‐printable rewritable PL paper was achieved. This study demonstrates the promise of dynamic insertion/extraction of ILs in hybrid chloroantimonates for anti‐counterfeiting and rewritable PL paper.