BaTiO3-coated Fe nanofibers are synthesized via a three-step process. α-Fe2O3 nanofibers with an average diameter of approximately 200 nm are first prepared using an electrospinning process followed by a calcination step. The BaTiO3 coating layer on the nanofiber is formed by a sol-gel process, and a thermal reduction process is then applied to the core-shell nanofiber to selectively reduce the α-Fe2O3 to Fe. The thickness of the BaTiO3 shell is controlled by varying the reaction time. To evaluate the electromagnetic (EM) wave-absorbing abilities of the BaTiO3@Fe nanofiber, epoxy-based composites containing the nanofibers are fabricated. The composites show excellent EM wave absorption properties where the power loss increases to the high frequency region without any degradation. Our results demonstrate that the BaTiO3@Fe nanofibers obtained in this work are attractive candidates for electromagnetic wave absorption applications.