Porous silica spheres functionalized with quaternary ammonium groups have been prepared by co-condensation of N-((trimethoxysilyl)propyl)-N,N,N-trimethylammonium chloride (TMTMAC) and tetraethoxysilane (TEOS) in the presence of cetyltrimethylammonium as a template and ammonia as a catalyst. The physicochemical characteristics of the resulting ion exchangers have been analyzed by various techniques and discussed with respect to the amount of organofunctional groups in the materials. For comparison purposes, both an ordered MCM-41 type mesoporous silica and two silica gels of different pore size have been grafted with TMTMAC. The ion-exchange capabilities were first evaluated from batch experiments (determination of anion-exchange capacities) and then by ion-exchange voltammetry at carbon paste electrodes modified with these hybrid materials. Effective concentration of Fe(CN)63- species in the anion exchangers was pointed out, while no significant accumulation of Ru(NH3)63+ was observed. The preconcentration efficiency was discussed on the basis of the organic group content in the materials as well as their structure and porosity. A second series of materials displaying zwitterionic surfaces was finally prepared and characterized with respect to their physicochemical properties and ion-exchange voltammetric behavior. They consisted of sulfonic acid-functionalized mesoporous silica samples resulting from the oxidation of thiol-functionalized silica spheres obtained by co-condensation of mercaptopropyl-trimethoxysilane (MPTMS) and TEOS, which were then grafted with TMTMAC at various functionalization levels. Possible interactions between the ammonium and sulfonate moieties in the confined medium were pointed out from X-ray photoelectron spectroscopy. The competitive accumulation−rejection of Fe(CN)63- and Ru(NH3)63+ redox probes was finally studied by cyclic voltammetry.