A spectroelectrochemical system assembled with a white light source, bifurcated optical fiber, Oriel Multispec spectrograph, and a charge-coupled device (CCD) detector is described. The system is shown to be capable of acquiring a whole spectrum in the spectral range of 290-800 nm in 25 ms or a longer period during electrochemical experiments at reflective working electrodes such as platinum or mercury. The utility of the system in studying electrochemical reactions during the potential scan, galvanostatic electrolysis, or after the potential step is demonstrated.