The in situ electrode potentials of anodes and cathodes in electrochromic (EC) devices were investigated. The solution-based 2-electrode EC device was fabricated with electrolyte solutions containing anodic and cathodic EC molecules. The electrochemical reaction in a 2-electrode EC device was controlled by the electrode reaction when electroactive molecules in smaller concentrations were used. In addition, the electrode showing less electrochemical activity in the EC device was subjected to larger overpotential under the application of a driving voltage, leading to the promotion of the redox reaction at the electrode. The results showed that the electrode potentials of the device were spontaneously regulated to facilitate both electrode reactions. It is very important to know the potential at each electrode in order to understand the reaction in detail in the 2-electrode EC device.