Co/BaTiO3 nanofibers with diameter of 100 nm have been successfully prepared using the novel electrospinning technique followed by subsequent reductive annealing treatment. The synthesized Co/BaTiO3 nanofibers were demonstrated to be polycrystalline with a double-phase heterostructure, containing both Co metal phase and BaTiO3 tetragonal phase by TEM, XPS and Raman spectroscopy analysis. Magnetization measurements revealed that the electrospun nanofibers had unique temperature-dependent magnetic properties. The simplicity and effectiveness of electrospinning make it a competitive approach to get one-dimensional heterogeneous nanostructure. The achievements shown here may also help to find new multiferroic materials. (C) 2014 Elsevier B. V. All rights reserved.