The combination of chirality and phase‐transition materials has broad application prospects. Therefore, based on the quasi‐spherical theory and the thought strategy of introducing chirality, we have successfully synthesized a pair of chiral enantiomeric ligands (R/S)‐triethyl‐(2‐hydroxypropyl)ammonium iodide, which can be combined with a tin hexachloride anion to obtain a pair of new organic–inorganic hybrid enantiomeric high‐temperature plastic phase‐transition materials: (R/S)‐[CH3CH(OH)CH2N(CH2CH3)3]2SnCl6 (1‐R/1‐S), which have a high temperature phase transition of Tc=384 K, crystallize in the P21 chiral space group at room temperature, and have obvious CD signals. In addition, compounds 1‐R and 1‐S have a good low‐loss dielectric switch and broadband gap. This work is conducive to the research into chiral high‐temperature reversible plastic phase‐transition materials, and promotes the development of multi‐functional phase‐transition materials. [ABSTRACT FROM AUTHOR]