A novel and facile preparation of activated hierarchical porous carbon spheres (AHPCS) with high surface area and developed pore structure from corn starch, a new precursor of carbon materials, via enzymolysis, carbonization and KOH activation was presented in this investigations, and AHPCS was then loaded with CoFe2O4 to fabricate magnetic AHPCS. Results showed that the composites had good magnetic properties and morphology, and the CoFe2O4 were mainly distributed in the macroporous. The saturation magnetization (Ms) increased with the CoFe2O4 content, while the surface area and pore volume decreased. The sample-3 (CoFe2O4:AHPCS = 1:75) possessed the surface area of 2110.48 (close to 2711.19 m(2) g(-1) of AHPCS) and Ms of 11.91 emu.g(-1), which were sufficient for magnetic separation in wastewater treatment. More than 97% methylene blue could be adsorbed in 5 min, and CoFe2O4/AHPCS composites could be separated from the solution easily by an outer magnet. (C) 2016 Elsevier B.V. All rights reserved.