Two smectites with different layer charge localization were used to characterize the chemical and structural aspects of minerals treated with 1.9 × 10−2m and 1 m heavy metal solutions (Zn2+ and Pb2+). Natural and treated smectites were analysed by: (1) X-ray powder diffraction first at 25°C and relative humidity of 60% and then at increasing temperature up to 400°C; (2) thermo-gravimetric and differential thermal analysis; (3) X-ray fluorescence; (4) atomic absorption and UV visible spectrophotometries. The sorption of both metals depends on 2:1 layer features and is enhanced when the total layer charge is mostly due to substitution in the octahedral sheet. The variability between Zn2+- and Pb2+-treated smectites in the interlayer water content depends both upon cation electrostatic features and upon smectite layer charge localization. The greatest water content was observed in [Zn2+]1 m-treated smectite showing charge imbalance in the octahedral sheet. In smectites treated with [Zn2+]1 m solutions, an additional thermal reaction occurs at a temperature of ∼380°C, and the d(001) spacing, which is 10 Å at a temperature of ∼200°C, gradually decreases in the temperature range 200–400°C. In smectites treated with 1 m [Pb2+] solutions this value is reached at a temperature of ∼150°C and remains quite constant up to 400°C.