This article describes the development and application of a new electrochemical methodology based on potential-modulated UV-vis reflectance spectroscopy (PMRS). The device configuration is based upon a thin-layer flow-through channel cell incorporating a platinum working electrode. Reagent solutions are pumped through the cell under well-defined hydrodynamic conditions and electrolyzed at the platinum working electrode. Measurements are presented for linear sweep and fixed de potentials with a superimposed small amplitude sinusoidal potential perturbation. A UV-vis source is employed to irradiate the electrode region, and the resulting reflected signal is analyzed using a phase sensitive detector. Experimental studies using tris(4-bromophenyl) amine (TBPA) in acetonitrile are presented which quantify the relationship between the absorption spectrum and reflected light intensity as a function of the transport rate, electrolysis reactions, and the modulation frequency of the incident irradiation. The experimental results are analyzed using numerical simulations based on a finite difference strategy. These permit the quantitative prediction of the concentration distribution of reagents within the cell. A fast Fourier transform (FFT) routine was used to analyze the frequency response of the numerically predicted reflectance signal. Excellent agreement was observed between the numerical predictions and experimental observations.