The experimental stability of four bentonites and one K-bentonite from Slovak deposits in the presence of iron was studied to simulate the possible reactions of clays (bentonite barrier) in the contact with Fe containers in a nuclear waste repository. The batch experiments were performed at 60 °C for 30 and 120 days in aerobic conditions. The reaction products were examined by XRD, FTIR, and Mössbauer spectroscopies and CEC (cation exchange capacities) were determined. Reaction solutions were analysed for selected elements using AAS (atomic absorption spectrometry). The results show that bentonites do not interact equally with metallic iron. Bentonites from the Jelsovy Potok, Kopernica and Lieskovec deposits reacted similarly whereas the interaction between the bentonite from Lastovce and the iron was less intensive. The lower reactivity of the bentonite from Lastovce can be explained by its low content of smectite. During iron-clay interactions the iron was consumed and Fe oxides (magnetite, lepidocrocite) were formed. Decrease of the smectite diffraction peaks intensity and CEC values during the experiments show rather the rearrangement of the original smectite crystals than dissolution of smectite. In the K-bentonite from the Dolna Ves deposit where the mixed-layer illite-smectite is present instead of smectite, the dissolution of illite-smectite was observed along with the neoformation of smectite. The structure of illite-smectite deteriorated more than the structure of smectites which suggests that this mixed-layer illite-smectite is much less stable in the presence of iron than smectites.