We study electron transfer associated with electrocatalytic reduction of hydrogen on single platinum nanoparticles separated from an electrode surface with an alkanethiol monolayer using a plasmonic imaging technique. By varying the monolayer thickness, we show that the reaction rate depends on electron tunneling from the electrode to the nanoparticle. The tunneling decay constant is similar to 4.3 nm(-1), which is small compared to those in literature for alkanethiols. We attribute it to a reduced tunneling barrier resulting from biasing the electrode potential negatively to the hydrogen reduction regime. In addition to allowing study of electron transfer of single nanoparticles, the work demonstrates an optical method to measure charge transport in molecules electrically wired to two electrodes.