Coal fly ash (CFA) has been extensively researched as an adsorbent for heavy metals, but its application is limited by its low adsorption capacity. The modification of CFA with hyperbranched polymers results in improved adsorption capacities. Hyperbranched polyethylenimine (HPEI) is a hyperbranched polymer containing NH 2 groups that can bind with heavy metal ions through complexation or electrostatic interactions. In this study, CFA−HPEI adsorbents with various HPEI loadings (1−5%) were prepared and evaluated for the removal of Cr(VI). The successful incorporation of HPEI onto CFA was confirmed using Fourier transform infrared, elemental analysis, and X-ray photoelectron spectroscopy (XPS). The 3% CFA−HPEI loaded adsorbent resulted in optimum results when the effect of pH and adsorbent dosage was studied. The pseudo-second-order kinetics model best described the adsorption kinetics at an initial concentration of 20 mg/L. The Freundlich adsorption isotherm model best fitted the equilibrium adsorption data with a maximum adsorption capacity of 85.93 mg/g. The Cr-loaded adsorbent was reused as a photocatalyst to degrade methylene blue (MB) in the presence of visible light. The loaded adsorbent degraded 98.9% of MB (5 mg/L) within 180 min and was accompanied by compounds with m/z of 173 and 234, corresponding to the intermediate degradation of Azure A. The XPS analysis confirmed the coexistence of Cr(III) and Cr(VI) on the surface of the adsorbent. In addition, the loaded adsorbent exhibited good stability following MB degradation with no structural changes observed. Thus, CFA−HPEI adsorbents can be utilized as low-cost adsorbents for the remediation of toxic Cr(VI) from water and wastewater. The Cr-loaded CFA−HPEI adsorbent can be effectively reused as a photocatalyst, thus reducing environmental pollution.