The　rational　electrode　design　is　one　of　the　most　important　ways　to　enhance　the　electrochemical　properties　of　lithium-sulfur　batteries　(LSBs).　In　this　contribution,　we　use　Ni-embedded　porous　graphitic　carbon　fiber　(PGCF@Ni)　as　the　scaffold　to　construct　a　novel　cathode　and　anode　for　LSBs.　With　the　help　of　elaborate　surface　engineering,　the　constructed　solid　electrolyte　interface　(SEI)@Li/PGCF@Ni　anodes　can　effectively　restrain　the　growth　of　lithium　dendrites　during　the　cycle,　exhibiting　an　ultralow　overpotential　of　∼10　mV　for　2000　h　at　1　mA　cm-2/1　mA　h　cm-2.　The　underlying　mechanism　is　further　investigated　by　COMSOL　Multiphysics　simulations.　Additionally,　the　PGCF@Ni/S　cathode　fabricated　by　the　molten　sulfurizing　method　manifests　superior　rate　performance　and　stability.　Ultimately,　the　assembled　SEI@Li/PGCF@Ni||PGCF@Ni/S　full　battery　exhibits　prominent　electrochemical　property　with　a　high　capacity　retention　of　about　77.9%　after　600　cycles　at　1　C.　Such　success　at　the　performance　improvement　in　LSBs　may　open　up　avenues　toward　other　rational　designs　of　high-quality　electrodes　in　electrochemical　energy　storage.　©　2022　American　Chemical　Society