A nanostructured electrode comprising a conductive electrode substrate having a surface functional group, a catalytic nanoparticle stabilized by a covalently-bound ligand bearing a peripheral functional group capable of interacting to the surface functional group, and a material capable of binding to the peripheral functional group. The conductive electrode substrate can be chemically modified and the surface functional group can create a layer of charge or chemical reactivity. The conductive electrode substrate can be chemically or electrochemically modified to create a surface functional group via covalent grafting capable of supporting multilayer deposition to create a layer of charge or chemical reactivity on the surface. The nanoparticle can be a platinum nanoparticle with covalently bonded negatively-charged ligands and the bridging material can be a polyelectrolyte.