—Selective sorption and/or fixation of cations with low hydration energies (e.g. K+, , Rb+, Cs+) by vermiculites is a well known phenomenon in soil science and it has been described by many investigators since the 1950s. Because most of the available studies deal with trioctahedral vermiculites, cation fixation in dioctahedral vermiculites is not as well understood as fixation by trioctahedral structures. The objective of the present study was to investigate the influence of saturation on the structure of a natural dioctahedral vermiculite. Because no dioctahedral vermiculite standard reference material was available, two natural dioctahedral vermiculite-rich soil clay samples were used in the study. The clays were saturated with using different protocols to simulate natural processes that likely take place in soils. The degree of fixation by the dioctahedral vermiculite was evaluated using X-ray diffraction, elemental N analysis, and infrared spectroscopy. All the treatments that involved saturation caused fixation and irreversible collapse (i.e. contraction to ~10 Å) of at least a portion of the previously hydrated (vermiculitic) interlayers. Air drying of the -saturated samples greatly enhanced the degree of the collapse. The results indicated that the collapse of dioctahedral vermiculite leads to the formation of a NH4-illite-like phase that is likely to occur in some soils and sediments that are rich in organic matter. The formation of a NH4-illite-like phase by fixation in vermiculitic interlayers needs to be taken into consideration in studies that deal with the clay mineralogy of sedimentary basins.