A sensitive potentiometric titration for vanadium (V) based effect of ligands such as nitrilotriacetic acid (NTA) and diethylenetriaminepenta-acetic acid (DTPA) are reviewed. The potential iron system decreased the presence of NTA and DTPA. In this case, iron (III) increased with respect to the vanadium (IV) volume. The production of iron (III)-ligand complex has increased. This result suggested that the formation of V(V)-NTA and V(V)-DTPA complexes were less favoured than that of V(IV)-NTA and V(IV)-DTPA complexes. The calculated correlation coefficients (r) conveyed the effectiveness of the graphite electrode as the indicator electrode for the potentiometric titrations. On comparing the potential jump values, the extent of potential caused by DTPA was found to be more than that of NTA. The utilization of graphite electrode has facilitated the potentiometric titration by significantly causing larger potential jump. This method was precise and accurate as no interference of foreign ions was observed. Hence, the approach could be applied to the vanadium (V) of any samples.