For organic-inorganic hybrid material, a change of dielectric constant always occurs in phase transition, which can be further controlled by temperature, light, pressure and etc. The design of organic-inorganic hybrid material with a significant dielectric change remains a challenge. Herein, an organic-inorganic hybrid material (TEACCl)2CuBr4 (TEACCl = (CH3CH2)3NCH2Cl+) with a distinct dielectric transition at 315.8 K was designed and constructed. Differential scanning calorimetry (DSC) test proved that there exists a reversible phase change at 315.8 K. Thermogravimetric (TG) measurement proved that it remained stable up to 505 K, exhibiting excellent stability. In addition, the single crystal structure, intermolecular interaction analysis and ultraviolet-vis spectral were discussed in this article.