The potentiostatic titration method is one of the effective methods for determining the total uranium assay in high-concentration uranium samples. A notable approach is the Devies-Grey titration method, which was first reported in 1964. In the U sample treatment process of this method, the reduction of U(VI) by Fe(II) is initially a non-spontaneous reaction based on the reduction potentials of the two half-reactions. However, in a high-concentration phosphoric acid medium, the reduction potential of Fe(II) is enhanced, simultaneously increasing the reduction potential of U(VI). As a result, the redox reaction becomes spontaneous due to these dual effects. On the other hand, the reaction kinetics can elucidate why nitric acid does not oxidize U(IV) during the oxidation of Fe(II) to Fe(III). Furthermore, the role of Mo(VI)/Mo(V) as a redox enhancer, employed alongside nitric acid, can be comprehended through electrochemical means. Similarly, the function of V(IV) as an electrochemical enhancer, aiding the action of the Cr(VI) titrant, becomes understandable. Grasping the various phenomena that manifest during the titration process is imperative for refining existing titration methods and pioneering new ones.