Three-dimensional porous Mn doped α-Fe2O3 nanostructures was successfully fabricated by calcined carbon spheres containing Fe(II) and Mn(II) ions, which obtained by hydrothermal treatment of glucose, Fe(II), and Mn(II) mixture solutions. The obtained nanostructures exhibit excellent ability in removal of Pb(II), Cr(VI), and As(III) ions from wastewater with easy magnetic separation.