Polyaniline (PANI) is recognized for its exceptional electrochemical conductivity, and its chemical structure, rich in amino and imine functional groups, exhibits significant removal capabilities for heavy metal pollutants in wastewater. In this study, PANI was synthesized via electrochemical cyclic voltammetry, and its micromorphology and phase structure were characterized using SEM, TEM, FTIR, and XRD. By modulating the polymerization potential, control over the surface morphology was achieved, thereby optimizing its adsorption performance. Additionally, the adsorption efficiency of electrochemically synthesized PANI for Cr(VI) in wastewater was assessed. Notably, in acidic conditions, PANI demonstrated an exceptionally high adsorption capacity for Cr(VI), reaching 130.1 mg/g. These findings highlight the potential of conductive polymers such as PANI in the development of highly efficient adsorbents for wastewater treatment, providing tangible solutions for addressing water pollution.