Two phlogopite, two mixed-layer phlogopite-vermiculite, and two vermiculite samples collected from the Palabora Complex of South Africa have been investigated at 295 K by X-ray diffraction, chemical analysis, and Mössbauer spectroscopy. In addition the temperature dependence of the Mössbauer spectra has been measured between 95 and 295 K for one phlogopite and one mixed-layer sample. The results of the chemical analyses and the Mössbauer spectra improve our knowledge of the vermiculitization process in the Palabora Complex. Both techniques indicate oxidation of the Fe ions during the sequence: phlogopite → mixed-layer → vermiculite. Further, the Mössbauer spectra indicate that Fe oxidation occurs mainly in the octahedral sites and suggest that migration and oxidation of the Fe2+ ions from the octahedral sites to the tetrahedral sites may occur during the transformation of phlogopite into a mixed-layer phase. Finally, the vermiculitization process involves both Fe oxidation and loss of K with a concomitant increase in the Mg content.