The dielectric behavior of rocks affected by the known phase transition of supercooled water is the main problem we analyzed. Three different granitic rocks were used to perform dielectric measurements in the frequency range from 100 Hz to 1 MHz and temperatures 100–350 K. Thin cylindrical samples were prepared, and circular electrodes were established using silver conductive paint. A clear change in the dielectric measurements appears at for one of the samples. This coincides with the known phase transition of supercooled water. Tightly bounded water confined in the pores of the rock do not crystallize at 273 K, but form a metastable liquid down to 200–220 K maintaining water polarization. Below this temperature, water molecules solidify and polarizability decreases. The rock presenting the most sizable change has a very low specific surface area of , has connected porosity of , and has the smallest degree of alteration. In addition, geochemical analyzes reveal a low percentage of hydration water in its structure confirming the role of pore water in this change. A comparison between water-saturated, oven-dried, and vacuum-dried samples was done. Finally, a logarithmic dependency of the critical temperature for the supercooled water phase transition with the measuring frequency was found.