The layered organic-inorganic hybrid of [NH3-(CH2)7-NH3]CaCl2Br2 has been synthesized from ethanolic solution by gradual cooling to room temperature. The reaction molar ratio is (1:1) organic/inorganic. Formation of the hybrid was confirmed by microchemical analysis, FTIR, and XRD. Thermal analysis DSC shows four transitions associated with solid-solid phase change, one major transition at T-3 = 330 +/- 2 K, entropy Delta S-3 = 13.65 J/mol-K associated with order-disorder phase transition, and three minor transitions at T-1 = 420 K, Delta S-1 = 0.19 J/mol-K, T-2 = 338 K, Delta S-2 = 0.85 J/mol-K, and T-4 = 319 K, Delta S-4 = 1.58 J/mol-K. Dielectric permittivity and AC conductivity as a function of temperature (295 < T(K) < 435) at selected frequencies (0.06 < f (kHz) < 20) are presented. Permittivity results indicate the presence of phase transition at T = 332 K. AC conductivity is thermally activated in different phases. The activation energy values range from 0.02 to 1.1 eV depending upon the temperature range and the applied frequencies. (C) 2017 Elsevier B.V. All rights reserved.