The expansivity of clayey soils is a complicated phenomenon which may affect the stability of geotechnical structures and geo-environmental projects. In all common factors for the monitoring of soil expansion, less attention is given to anion type of pore space solutions. Therefore, this paper is concerned with the impact of various concentrations of different inorganic salts including NaCl, $Na_2SO_4$, and $Na_2CO_3$ on the macro and microstructure behavior of the expandable smectite clay. Comparison of the responses of the smectite/NaCl and smectite/$Na_2SO_4$ mixtures indicates that the effect of anion valance on the soil engineering properties is not very pronounced, regardless of the electrolyte concentration. However, at presence of carbonate as potential determining ions (PDIs) the swelling power increases up to 1.5 times compared to sulfate or chloride ions. The samples with $Na_2CO_3$ are also more deformable and show lower osmotic compressibility than the other mixtures. This demonstrates that the barrier performance of smectite greatly decreases in case of anions with the non-specific adsorption (e.g., $Cl^-$ and $SO{_4}^{2-}$) as the salinity of solution increases. Based on the results of the X-ray diffraction and sedimentation tests, the high soil volumetric changes upon exposure to carbonate is attributed to an increase in the repulsive forces between smectite basic unit layers due to the PDI effect of $CO{_3}^{2-}$ and increasing the pH level which enhance the buffering capacity of smectite. The study concluded that the nature of anion through its influence on the re-arrangement of soil microstructure and osmotic phenomena governs the hydro-mechanical parameters of expansive clays. It seems not coinciding with the double layer theory of the Gouy-Chapman double layer model.