To remove antimony (Sb) ions from water, a novel composite adsorbent was fabricated from ferriferous oxide and waste sludge from a chemical polishing process (Fe3O4@HCO) and encapsulated in sodium alginate (SAB). The SAB adsorbent performed well with 80%−96% removal of Sb (III) ions within a concentration range of 5−60 mg/L. The adsorption mechanism of Sb (III) was revealed to be the synergy of chemisorption (ion exchange) and physisorption (diffusion reaction). The adsorption isotherms and kinetics conformed to the Langmuir isotherm and the pesudo-second-order kinetic model. Both initial pH and temperature influenced the adsorption performance with no collapse of microbeads within solution pH range 3−7. Most importantly for practical applications, these microspheres can be separated and recovered from aqueous solution by a magnetic separation technology to facilitate large-scale treatment of antimony-containing wastewater.