Water pollution due to industrial processes has necessitated and spurred robust research into the development of adsorbent materials for remediation. Polyphenylenediamines (PPD) have attracted significant attention because of their dual cationic and redox properties. They are able to reduce Cr(VI) to Cr(III) in solution. Interrogation of the chemical processes involved in the Cr(VI) adsorption on para-PPD was primarily by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectroscopy. It was confirmed that the underlying oxidation of the amino groups to imines during the reduction of Cr(VI) to Cr(III) was irreversible. This process occurred at both acidic and alkaline conditions. Reduction was accompanied by Cr(III) chelation on the adsorbent surface. Further, regeneration with dilute aqueous NaOH and HCl extended the polymer's adsorptive capacity beyond exhaustion of its redox potentials.