Rechargeable batteries employing aqueous electrolytes are more reliable and cost-effective as well as possess high ionic conductivity compared to the flammable organic electrolyte solutions. Among these types of batteries, aqueous batteries with multivalent ions attract more attention in terms of providing high energy density. Herein, electrochemical behavior of an organic electrode based on a highly aromatic polymer containing 2,3-diaminophenazine repeating unit, namely poly(ortho-phenylenediamine) (PoPD), is tested in two different multivalent ions (Zn2+ and Al3+) containing aqueous electrolytes, that is, in zinc sulfate and aluminum chloride solutions. PoPD is synthesized via electropolymerization, and its ion transport and storage mechanism are comprehensively investigated by structural and electrochemical analyses. The electrochemical quartz crystal microbalance, time-dependent Fourier transform infrared, and electrochemical impedance spectroscopy analyses as well as ex situ X-ray diffraction observations established that along with the Zn2+ or Al3+ ions, reversible proton insertion/extraction also takes place. Contrary to the most of the organic electrodes that requires the use of conductive carbon additives, the electrodeposited PoPD electrode is intrinsically electrically conductive enough, resulting in a binder and additive free electrode assembly. In addition, its discharge products do not dissolve in aqueous medium. As a whole, the resulting PoPD electrode delivers excellent rate performances with prolonged cycle life in which discharge capacities of ∼110 mAh g–1 in 0.25 M AlCl3 and ∼93 mAh g–1 in 1 M ZnSO4 aqueous electrolyte after 1000 cycles at a current density of 5C have been achieved.