A new method to grow a well-ordered epitaxial ZnFe2O4 thin film on Al2O3(0001) substrate is described in this work. The samples were made by annealing the ZnO/Fe3O4 multilayer which was grown with low energy ion beam sputtering deposition. Both the Fe3O4 and ZnO layers were found grown epitaxially at low temperature and an epitaxial ZnFe2O4 thin film was formed after annealing at 1000 degrees C. X-ray diffraction shows the ZnFe2O4 film is grown with an orientation of ZnFe2O4(111)//Al2O3(0001) and ZnFe2O4(1-10)//Al2O3(11-20). X-ray absorption spectroscopy studies show that Zn2+ atoms replace the tetrahedral Fe2+ atoms in Fe3O4 during the annealing. The magnetic properties measured by vibrating sample magnetometer show that the saturation magnetization of ZnFe2O4 grown from ZnO/Fe3O4 multilayer reaches the bulk value after the annealing process. (C) 2010 Elsevier B.V. All rights reserved.