The [(CH3)3NH]CdCl3 compound was obtained by slow evaporation at room temperature and characterized by X-ray powder diffraction patterns, differential scanning calorimetry, and impedance spectroscopy. This compound was found to crystallize in the orthorhombic system with Pbnm space group and was characterized by four phase transitions (T 1 = 355 K, T 2 = 372 K, T 3 = 415 K, and T 4 = 446 K). The analysis of Nyquist plots has revealed the contribution of two electrically active regions corresponding to the bulk mechanism and distribution of grain boundaries. The modulus plots were characterized by the presence of two peaks associated with the grain and grain boundaries. Thermodynamic parameters such as the free energy for dipole relaxation ΔF, the enthalpy ΔH, and the change in entropy ΔS have been determined with the help of the Eyring theory. The temperature dependence of the electrical conductivity (σ g ), σ dc , and f p confirms the observed transitions in the calorimetric study.