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Vanadium redox flow batteries (VRFB) suffer from capacity fades owing to side reactions and crossover effects through the membrane. These processes lead to a deviation of the optimal initial average oxidation state (AOS=+3.5) of vanadium species in both half‐cell electrolytes. To rebalance the electrolyte solutions, it is first necessary to determine the current AOS. In this study, a new method was developed that enables an accurate determination of the AOS. A potential‐step analysis was performed with mixed electrolyte solutions of both half‐cells during the initial charging. The potential was recorded with a simple open‐circuit voltage (OCV) cell, and the potential‐steps were analyzed. A correlation between the duration of the potential plateaus in the OCV and the amount of vanadium ions of a certain oxidation state in the half‐cell electrolytes was found and used to precisely determine the AOS with a maximum error of 3.6 %.