UV-vis reflection spectroelectrochemistry has proven to be a very useful multiresponse technique to evaluate the quality of bismuth films obtained by electrochemical deposition on glassy carbon electrodes (GCEs). Bismuth films have recently emerged as a promising and environmental friendly alternative to mercury electrodes for stripping analysis. Spectroelectrochemical measurements, carried out in a flow cell, allowed us to follow in situ the electrodeposition and stripping of bismuth and cadmium. Electrochemical and spectroscopic responses individually have led to successfully quantify the amount of cadmium in test solutions.