Porous sulfonic acid functionalized silica spheres have been prepared by oxidation of thiol-functionalized mesoporous silica samples obtained by co-condensation of (mercaptopropyl)trimethoxysilane and tetraethoxysilane in the presence of cetyltrimethylammonium as a template. The physicochemical characteristics of the resulting ion exchangers have been analyzed by various techniques and discussed with respect to the amount of functional groups in the materials. Their ion exchange behavior was then studied from batch experiments (determination of cation exchange capacities) and by electrochemistry at carbon paste electrodes modified with these solids. In particular, ion exchange voltammetry applied to two model electroactive cations, Cu2+ and Ru(NH3)63+, has pointed out the key role played by the content of organofunctional groups in the materials (which strongly affects their structure and porosity) on their performance as electrode modifiers for preconcentration of target analytes prior to electrochemical detection.