We investigated the structural, vibrational, and electrical transport properties of natural kaolinite and its high-pressure polymorphs by Raman scattering and electrical conductivity measurements at 293–673 K and up to 10.0 GPa using diamond-anvil cell. Upon compression, kaolinite underwent two structural transitions from kaolinite I to kaolinite II to kaolinite III phases at pressures of 2.9 and 6.5 GPa, respectively, which was disclosed by the inflection point in the pressure-dependent Raman shifts and electrical conductivity. Upon decompression, kaolinite III directly transformed to kaolinite I at 0.8 GPa without the appearance of kaolinite II. Additionally, the influence of temperature on the structural transformation of natural kaolinite was explored by high-temperature and high-pressure electrical conductivity measurements and negative temperature-dependent transition pressure correlations were obtained. A phase diagram of natural kaolinite was established for the first time and the kaolinite I-kaolinite II and kaolinite II-kaolinite III phase transition boundaries were determined: P (GPa) = 4.298–0.00462 T (K) and P (GPa) = 8.895–0.00799 T (K), respectively. Furthermore, our acquired phase diagram can be applied to understand the stability field of high-pressure polymorphs of kaolinite in the Earth’s interior and may provide a phase transition model for other kaolin-group minerals.