The current investigation delves into the effectiveness of dimethylaminopropylamine tethered onto polystyrene‐co‐divinylbenzene polymer for the proficient elimination of hexavalent chromium from simulated wastewater. The resin was characterized using SEM, FT‐IR spectroscopy, EDX, elemental analysis, thermogravimetry, and solid state 13C NMR spectroscopy. The experimental investigation into sorption dynamics involved varying process parameters, including initial Cr(VI) concentration, amount of adsorbent used, solution pH, temperature, and contact between phases. The binding modes of chromate ions, either bidentate or monodentate, were observed, with their manifestation influenced by the solution's pH. Sorption capacity was found to be pH‐dependent, with removal efficiencies of 98.27%, 96.38%, and 85.52% observed at pH levels of 3, 6, and 9, respectively. PS‐DMAPA resin demonstrated robust regeneration capabilities, throughout five consecutive adsorption–desorption cycles. The Langmuir adsorption model exhibited excellent agreement with the experimental findings (R2 = 0.9994), revealing a maximum adsorption capacity of 70.15 mg g−1 at 298 K. Additionally, the experimental findings closely matched the second‐order kinetic model. The kinetics of sorption and the thermodynamic parameters were also investigated. Performance evaluating of the PS‐DMAPA resin under dynamic conditions included analyzing the Cr(VI) breakthrough curve. The 10% sodium chloride solution was employed to effectively recover the extracted Cr(VI) quantitatively.