Porous graphene-doped carbon/Fe3O4 (GN@C/Fe3O4) nanofibers are synthesized via in-situ electrospinning and subsequent thermal treatment for use as lithium-ion battery anode materials. A polyacrylonitrile (PAN)/polymethyl methacrylate (PMMA) solution containing ferric acetylacetone and graphene oxide nanosheets is used as the electrospinning precursor solution. The resulting porous GN@C/Fe3O4 nanofibers show unique dark/light banding and a hierarchical porous structure. These nanofibers have a Brunauer–Emmett–Teller (BET) specific surface area of 323.0m2/g with a total pore volume of 0.337cm3/g, which is significantly greater than that of a sample without graphene and C/Fe3O4 nanofibers. The GN@C/Fe3O4 nanofiber electrode displays a reversible capacity of 872 mAh/g at a current density of 100mA/g after 100 cycles, excellent cycling stability, and superior rate capability (455mA/g at 5A/g). The excellent performance of porous GN@C/Fe3O4 is attributed to the material’s unique structure, including its striped topography, hierarchical porous structure, and inlaid flexible graphene, which not only provides more accessible active sites for lithium-ion insertion and high-efficiency transport pathways for ions and electrons, but also accommodates the volume change associated with lithium insertion/extraction. Moreover, the zero-valent iron and graphene in the porous nanofibers enhance the conductivity of the electrodes.