By a carbon nanotube (CNT) spatially confined metal-catalyzed structural reconstruction, carbon nanofibers (CNFs) with a hollow, hollow-solid, solid graphite core, and CNT shell are prepared using nitrogen heterocycle (NHC) and polycyclic aromatic hydrocarbon (PAH) as carbon sources. The formation mechanism of CNFs with oriented graphene layers and enlarged intergraphene spacing is studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction analysis. It revealed that this one-dimensional nanoconfined metal-catalyzed carbon rearrangement is totally different from the reported spatially localized metal-catalyzed graphitization of electrospun polymer and nanocasted carbohydrate nanofibers, as the graphene orientation, cavity volume, and interlayer distance of CNFs can be controlled by the carbon concentration-related competitive metal-catalyzed tip growth of latitudinal and longitudinal graphene layers from NHC and PAH. The unique CNF structure renders good electronic/ionic conductivity, abundant Li