This work is focused on the mechanistic aspects of the redox behavior of poly(azure A) taking advantage of the controlled modulation of their oxidation states by ac-electrogravimetry. The originality of this technique is its ability to discriminate between cation and anion involved in the charge compensation process and the accompanying free solvent transfer, directly or indirectly. Two processes were proposed where the faster ionic exchange is considered to be the participation of the anion species acting as counterions whereas the slower one is related to the proton transfer. The proton is implied as reactants for the two electroactive sites identified in the polymer chain, the intermonomeric amino links and the aromatic rings. The ac-electrogravimetry technique was used to study the kinetic aspects of the transfer of proton (H(+)), anion (NO(3)(-) or Cl(-)), and free solvent in KNO(3) and KCl aqueous solutions.