Magnetically separable ternary hybrid ZnFe2O4-Fe2O3-Bi2WO6 hollow nanospheres were designed and synthesized by an effective three-step approach. Specifically, using phenolic formaldehyde microspheres (PFS) as template direct the sequential coating of alpha-Fe2O3/ZnFe2O4 layer and subsequent Bi2WO6 layer via impregnating-calcination process. The photocatalytic activity under visible light irradiation is in the order of ZnFe2O4-Fe2O3-Bi2WO6 > ZnFe2O4-Fe2O3-Bi2WO6 >Bi2WO6 > ZnFe2O4-Fe2O3 > ZnFe2O4. The enhanced activity could be attributed to the cascade electron transfer from ZnFe204 to ce.-Fe203 then to Bi2WO6 through the interfacial potential gradient in the ternary hybrid conduction bands, which facilitate the charge separation and retard the charge pair recombination. Furthermore, the ternary hybrid ZnFe2O4-Fe2O3-Bi2WO6 hollow nanospheres could be conveniently separated by using an external magnetic field, and be chemically and optically stable after several repetitive tests. The study also provides a general and effective method in the composite hollow nanomaterials with sound heterojunctions that may show a variety of applications. (C) 2014 Elsevier B.V. All rights reserved.