Bipolar electrochemistry is receiving growing attention in the last years, not only because it is an important tool for studying electron transfer processes, but also because it is really fruitful in the development of new analytical sensors. Bipolar electrodes show promising applications as a direct analytical tool since oxidation and reduction reactions take place simultaneously on different parts of a single conductor. There are several electrochemical devices that provide information about electron transfer between two immiscible electrolyte solutions, but to the best of our knowledge, this is the first time that a bipolar device is able to record two spectroelectrochemical responses concomitantly at two different compartments. It allows deconvolving the electrochemical signal into two different optical signals related to the electron transfer processes occurring at two compartments that are electrically in contact. The combination of an electrochemical and two spectroscopic responses is indeed very useful, providing essential advantages in the study of a huge variety of systems. The study of three different electrochemical systems, such as reversible redox couples, carbon nanotubes, and conducting polymers has allowed us to validate the new cell and to demonstrate the capabilities of this technique to obtain valuable time-resolved information related to the electron transfer processes.