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+　storage　interlayer　gaps,　and　robust　mechanical　durability,　resulting　in　outstanding　electrochemical　properties　as　anodes　in　lithium-ion　batteries.　The　optimum　CNF　anode　delivers　a　stable　discharge　capacity　of　475　mA　h　g-1　at　0.1　C,　an　extraordinary　rate　capability　of　303　mA　h　g-1　at　5　C,　and　a　remarkable　long-term　cycling　stability　of　378　mA　h　g-1　after　600　cycles　at　1　C.　This　1D　nanoconfined　metal　catalysis　synthesis　could　be　useful　for　the　development　of　efficient　CNF　anodes　in　many　electrochemical　reactions　with　a　potential　for　industrial　applications.　©　2025　American　Chemical　Society.