The electrochemical measurement of multivalent cations concentration (EM2C2) technique was demonstrated to simultaneously determine the concentration of the redox pair V(IV)/V(V) in aqueous solutions. This technique consists of measuring the current at an applied potential under diffusion transport using a rotating disk electrode. The influence of several parameters such as scan rate potential, rotation rate of the electrode, and interferences in the measurements were investigated. Different linear equations derived from these parameters were compared to improve the analysis. Detection limits using the EM2C2 methodology were 1 mM for V(IV) and >1 mM for V(V) making the methodology suitable to perform the measurement of vanadium speciation with relative ease and less time at low cost.