Tetravalent metal acid (TMA) salts are cation exchangers due to the presence of structural hydroxyl groups. The presence of protons makes the TMA salt, a potential candidate for solid state protonic conduction. In the present endeavour, amorphous inorganic ion exchangers of the class of TMA salts, tin tungstate (SnW), titanium tungstate (TiW) and zirconium tungstate (ZrW) have been synthesized and characterized for elemental analysis, thermal analysis (TGA, DSC), FTIR spectroscopy and X-ray analysis. Chemical resistivity of these materials have been assessed in various acidic, basic and organic media. Ion exchange capacity has been determined and effect of heating on ion exchange capacity has been studied. The proton conduction behaviour of these materials has been studied by measuring specific conductance (σ) at different temperatures in the range 30–175°C using HP 4192 A impedance analyzer. The specific conductance values for the three materials have been compared.