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.