FeCO 3 is a potential anode material, owing to advantages such as facile synthesis, low cost, and abundant natural resources, but its poor cyclic stability and low rate performance seriously limit practical applications in lithium-ion batteries (LIBs). In this paper, the sheath/core hybrid of FeCO 3 /carbon nanofibers (CNFs) as a binder-free anode for high-performance LIBs has been synthesized by using a facile hydrothermal method. Porous FeCO 3 nanosheets grow in a stable manner on the surface of CNFs, and the flexible FeCO 3 /CNF film gives a specific surface area as high as 302.6 m 2 g À1 . The FeCO 3 /CNF film, with its porous architecture, provides open and continuous channels for fast diffusion of Li + to the active material of FeCO 3 , whereas the CNFs effectively play the leading role as the conductive core to efficiently transfer electrons for rapid lithiation/delithiation of FeCO 3 , and offer a buffering network to reduce the volume change during cycling. The hybrid FeCO 3 /CNF film, as a binderfree anode, delivers 592.2 mAh g À1 at the 3rd cycle and 546.2 mAh g À1 at the 200th cycle. As a comparison, bare FeCO 3 drops to 101 mAh g À1 at the 200th cycle. At a current density of 2 Ag À1 , FeCO 3 /CNF delivers 308.2 mAh g À1 , which is far higher than the 11 mAh g À1 of bare FeCO 3 and 52 mAh g À1 of bare CNFs. The FeCO 3 /CNF film presents an applicable hybrid structure as a binder-free anode material for ultrathin and ultralight energy-storage devices.