Differential scanning calorimetry (DSC) and differential thermal analysis (DTA) are performed for the compound (n-C12H25NH3)2CdCl4. The ac conductivity σ(ω,T), and the complex dielectric permittivity ϵ*(ω,T) are measured as a function of temperature (100 K < T < 375 K) and at some selected frequencies (3 → 100 kHz). Two structural phase transitions are detected at T = (330 ± 1) K and T = (343 ± 1) K as minor and major transitions, respectively. The analysis of the measured electrical parameters reveals that the frequency-dependent conductivity obeys the power law, and the quantum mechanical tunneling (QMT) model is the main conduction mechanism in the low-temperature phase (LTP; phase III). The role of hydrogen bond N–H…Cl as a trigger force for phase transitions has been discussed. While the LTP is of the order–disorder type, the high-temperature phase (HTP) or phase I seems to be conformational and represents the main transition.