Cu2+/Cu+–[Fe(CN)6]3-/[Fe(CN)6]4- redox couple is investigated for energy storage applications. Analogous to Pourbaix diagram, Potential – Time plot indicating regions such as Nernstian, Steady state and Redox were analyzed. Appropriate electrochemical reactions associated with these regions were also attempted. The redox couple provides power continuously for 3312 h with good stability. The coulombic, voltage and energy efficiencies obtained were 96%, 72.13% and 69.3% respectively. The maximum voltage attained by the cell is 0.88 V. The baseline voltage of the cell is 0.3 V and never reaches zero voltage output even after the inactivity of anolyte. Hence by replenishing the anolyte and anode, the device can be made functional for next 3312 h without replacing catholyte. Thus Cu2+/Cu+–[Fe(CN)6]3-/[Fe(CN)6]4- redox couple can be a low cost alternative or partial substitution redox couple to improve the performance of flow batteries.