Abstract: The conversion of Malawi vermiculite into K-vermiculite by treatment with bi-ionic K-Mg solutions of 1 N total ion concentration (KCl and MgCl2 mixed solutions of ionic strength equal to 0.5) was studied by following the 00l X-ray powder diffraction (XRD) reflections. Flakes of Mg-saturated samples were treated at 160°C during 24 hr with bi-ionic solutions, with the K concentration varying from zero to pure 1 N KCl solution. The K-Mg interlayer exchange began at a critical value xK = .0196 (K/Mg = 1/100) of the molar fraction of K in the solution. Above the critical concentration and extending to pure 1 N KCl, the XRD diagrams were characteristic of a 10-Å/14-Å interstratification that had a marked tendency towards regularity. Experiments with KCl and MgCl2 mixed solutions of ionic strength equal to 0.75 and 1.0 showed that the exchange began at the same critical value xK as the experiments with ionic strength equal to 0.5, if the K added was equivalent. X-ray fluorescence analysis further showed that the amount of K adsorbed was proportional to the molar fraction xK and to the proportion of K-saturated layers (10 Å) in the interstratification. To explain the mechanism of this quasi-regular interstratification, a crystallochemical rather than a thermodynamic mechanism is proposed.