Dual phase transition/switch materials are a critical cornerstone of information storage and sensing. However, they are difficult to design successfully, and compared with materials showing single-switchable phase transitions, the dual ones retain many challenges by far. Therefore, the significance of a general strategy is far greater than an accidental success. Here, an efficient strategy combining branchlike Et3R and trunklike benzylamine analogues successfully validates dualswitch implementation in the dielectric materials. This inevitable success is based on our treelike analogue mentioned above in which amines with multiple branches can achieve a temperature-induced phase change. Exactly, (BCDA)(2)ZnBr4 [BCDA = benzyl-(2-chloroethyl)-dimethylammonium] proves the regularity and undergoes two reversible phase transitions at 295.4 and 340.8 K, respectively. Variable-temperature single-crystal X-ray diffraction revealed that the generation of double phase transitions is caused by progressive changes of treelike BCDA(+) as the temperature rises. Because the permittivity epsilon' of (BCDA)(2)ZnBr4 abruptly changed near the phase-transition temperatures, such physical properties make it have latent applicability. In short, the success of our strategy will inspire researches to discover more interesting dual phase transition/switch materials.