In-depth evaluation of the electrochemical performance of all-vanadium redox flow batteries (VRFBs) under operando conditions requires the insertion of a reliable reference electrode in the battery cell. In this work, an easy-to-make reference electrode based on silver–silver sulfate is proposed and described for VRFBs. The relevance and feasibility of the information obtained by inserting the reference electrode is illustrated with the study of ammoxidized graphite felts. In this case, we show that the kinetic of the electrochemical reaction VO2+/VO2 + is slower than that of V2+/V3+ at the electrode. While the slow kinetics at the positive electrode limits the voltage efficiency, the operating potential of the negative electrode, which is outside the stability widow of water, reduces the coulombic efficiency due to the hydrogen evolution.