The boundaries of what can be measured electrochemically have been advanced by recent progress in nanoconfinement techniques, amplification strategies, and electrochemical instrumentation. Such developments have made it possible to measure electrochemical processes involving small amounts of charge being passed over short periods of time, down to currents on the order of femtoamps. However, the White group recently demonstrated that the inherent stochastic motion of electrons (i.e. shot noise) produces a practical electrochemical limit of quantification of 2100 electrons, which corresponds to a charge of ≈ 0.34 femtocoloumbs. Furthermore, the presence of background currents and the shortcomings of instrumentation in experimental electrochemistry push this limit of quantification to higher values. As a result, several literature examples of low-current electrochemistry were shown to have come very close to the limit of quantification, highlighting the need to find ways of boosting the sensitivity of electron counting for future progress in fields such as nanoelectrochemistry and single-entity electrochemistry. One possible method of overcoming the detection limit is to employ the enhanced sensitivity of photon detection, which can be performed down to single molecule and single photon levels, by using an electrochemically induced luminescent signal to report on charge transfer processes.