The chemical confinement of a pH sensitive fluorophore to a thin-reaction layer adjacent to an electrode surface is explored as a potentially innovative route to improving the spatial resolution of fluorescence electrochemical microscopy. A thin layer opto-electrochemical cell is designed, facilitating the visualization of a carbon fiber (diameter 7.0 μm) electrochemical interface. Proton consumption is driven at the interface by the reduction of benzoquinone to hydroquinone and the resulting interfacial pH change is revealed using the fluorophore 8-hydoxypyrene-1,3,6-trisulfonic acid. It is demonstrated that the proton depletion zone may be constrained and controlled by the addition of a finite acid concentration to the system. Simulation of the resulting fluorescence intensity profiles is achieved on the basis of a finite difference model, with excellent agreement between the theoretical and experimental results.