Nanostructured materials enable the development of miniature sensing devices that are compact, low-cost, low-energy-consumption, and easily integrated into field-deployable units. Recently we have successfully developed electrochemical sensors based on functionalized nanostructured materials for the characterization of metal ions. Specifically, glycinyl-urea self-assembled monolayer on nanoporous silica (Gly-UR SAMMS) has been incorporated in carbon paste electrodes for the detection of toxic metals such as lead, copper, and mercury based on adsorptive stripping voltammetry, while acetamide phosphonic acid self-assembled monolayer on nanoporous silica (Ac-Phos SAMMS) has been used for the detection of uranium. Both electrochemical sensors yield reproducible measurements with excellent detection limits (at ppb level), are selective for target species, does not require the use of mercury film and chelating agents, and require little or no regeneration of electrode materials. The rigid, open, paralleled pore structure combined with suitable interfacial chemistry of SAMMS also results in fast responses of the electrochemical sensors.