Alkylammonium ion exchange, x-ray powder diffraction (XRD), x-ray fluorescence spectroscopy (XRF), and high resolution transmission electron microscopy (HRTEM) have been used to study the chemistry and the physical properties of illite/smectite (I/S) clays from Paleozoic K-bentonites. The data have been used to evaluate current models of I/S interstratification and the mechanism of formation of illite during bentonite diagenesis.