Display omitted •Hydrophilic Ce@SCA were designed and synthesized through facile method.•The hydrophilicity of the carbon aerogel microspheres was improved.•Ce@SCA possesses excellent adsorption properties and selectivity for Sb(III) in water.•Redox and complexation processes are involved in the removal mechanisms of Sb(III).•DFT calculations confirm the positive effect of sulfur doping on the adsorption process. Antimony pollution is well recognized to induce cancer and deformity. By polymerization technique, a carbon aerogel microsphere (Ce@SCA) modified by Ce and S with micron size, well-developed pore structure, and large specific surface area was created. Ce@SCA exhibited the advantages of efficient selectivity and high adsorption capacity for Sb(III) in water. The highest adsorption capacity derived using the Sips isothermal model was 345.18 mg∙g−1, and the Sb (III) adsorption process was thermodynamically estimated as spontaneous, exothermic, and entropy-decreasing chemisorption. Meanwhile, Ce@SCA can convert highly toxic Sb(Ⅲ) into Sb(Ⅴ), which is suitable for the remediation of antimony-contaminated water bodies. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) were analyzed to elucidate the adsorption mechanism and to propose optimized adsorption configurations. A considerable number of –OH and -SH on the surface may increase the binding site of Sb, and the creation of S-Sb, O-Sb, and Ce-O-Sb covalent bonds was the key to Sb adsorption. This research provides a simple method for preparing cerium oxide-loaded and sulfur-doped carbon aerogel (Ce@SCA) with mild conditions and no hazardous waste, which also has superior adsorption properties for Sb (III) and high reusability.