With increasing groundwater and surface water contamination due to improper discharge of chromium-laden wastewaters, it is compelling to synthesize a material that can selectively remove Cr(VI) from the impaired water at neutral or near-neutral pH. In this study, various composites were synthesized through chemical grafting of polyethylenimine (PEI) polymer on the surface of INDION PA 800 polystyrene beads by varying the PEI loading and glutaraldehyde (GA) crosslinking for Cr(VI) removal. The adsorbent called PS-7 with 16% PEI and 2.5% GA crosslinking performed best, demonstrating Cr(VI) removal greater than 99% even at pH 9. The adsorbent showed significant trace Cr(VI) removal from the impaired solution containing competing anions at 500 times the concentration of Cr(VI) at neutral pH. Further, 1.0 g/L adsorbent showed 100% Cr(VI) removal from a solution containing 5 mg/L Cr(VI) at pH 7 and 9. PS-7 showed significant adsorption capacity of 355.26 and 143.6 mg/g for fixed-bed column runs at influent pH 3 and 5, respectively. An insightful investigation revealed that the use of hydrophobic matrix for PEI immobilization played an important role in Cr(VI) removal at neutral pH, as opposed to the other reported PEI-based adsorbents with hydrophilic matrix which were capable of removing chromate anions at acidic pH only. The phenomenon of redox reaction occurring in the adsorbent was validated by X-ray photoelectron spectroscopy, where Cr(VI) was reduced to Cr(III) with the help of electron-donating NH2 groups and the adsorbent got oxidized. Thus, PS-7 adsorbent holds immense potential for treating real-life Cr(VI)-contaminated waters. © 2022 Elsevier Ltd