Smectites from the E horizon of podzols dated at 1200–10,000 y in central and northern Finland were studied. Clay minerals in the fine (<0.1 μm) and coarse (0.1–2 μm) fractions were examined by X-ray diffraction. The distribution (octahedral or tetrahedral) and magnitude of the layer charge of expandable minerals were estimated using intercalation of alkylammonium ions (nC = 12) associated with the Hofmann & Klemen effect. In addition, charge alteration following desaturation (H+ exchange) and autotransformation was investigated. Smectites from the E horizons of podzols are not homogeneous but constitute a mixture of several populations with various layer charges. Smectites with lower layer charge are present in podzols having a longer effective time of pedogenesis, suggesting alteration of the high-charge smectites with time. Experimental alteration of the smectites by autotransformation shows that a decrease of the layer charge is easily produced by desaturation of the smectite clays.