A kaolinite-tetrabutylphosphonium bromide (TBPBr) intercalation compound (Kaol-TBPBr) was prepared from kaolinite providing inorganic aluminosilicate layers and TBPBr as intercalated salts between the layers through the use of an intermediate, a kaolinite-dimethylsulfoxide (DMSO) intercalation compound (Kaol-DMSO). The experimental data through complementary techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, solid-state 13C and 29Si nuclear magnetic resonance (NMR) spectroscopy with cross polarization and magic angle spinning, inductively coupled plasma emission spectrometry, and ion chromatography, indicate complete removal of DMSO and intercalation of TBPBr with an increase in the basal spacing from 1.12 nm (Kaol-DMSO) to 1.53 nm (Kaol-TBPBr). In contrast to a similar intercalation compound, a kaolinite-tetrabutylammonium bromide (TBABr) intercalation compound (Kaol-TBABr) with a basal spacing of 1.51 nm, Kaol-TBPBr displayed interesting features such as enhanced thermal stabilities as well as bold resistance against several solvents. Kaol-TBPBr withstood thermal decomposition of the organic species over 100 °C much better than Kaol-TBABr. When Kaol-TBPBr and Kaol-TBABr were refluxed in methanol, ethanol, acetone, or toluene for 1 day, Kaol-TBPBr preserved the expanded kaolinite layers, while the Kaol-TBABr structure completely collapsed due to the release of TBABr. Thus, with these particular and unique features of Kaol-TBPBr, organophosphonium salts appear to be promising guest species for intercalation chemistry of kaolinite.