The　electrocatalytic　sulfur　oxidation　reaction　(SOR),　marked　by　a　multifaceted　16-electron　transfer,　stands　as　a　pivotal　advancement　in　lithium-sulfur　battery　technology.　In　this　process,　the　initial　conversion　of　Li2S　to　Li2S2　during　the　charging　phase　is　identified　as　the　rate-determining　step,　characterized　by　a　significant　energy　barrier.　The　integration　of　a　nanoflower-shaped　transition　metal　selenide　catalyst　on　carbon　(FeSe2@C)　catalyzes　the　SOR.　The　synergistic　effect　of　d-p　orbital　hybridization　in　the　Fe-S　bond　and　the　redox　cycling　between　Fe2+　and　Fe3+　facilitates　electron　transfer,　thereby　lowering　the　decomposition　barrier　of　Li2S.　This　has　been　confirmed　through　both　density　functional　theory　(DFT)　calculations　and　experimental　electrocatalysis.　The　oxidation　of　Li2S　is　reliant　on　an　efficient　charge　transfer　mechanism,　where　electrons　are　progressively　transferred　to　intermediate　species,　leading　to　direct　interactions　with　Li2S　and　the　formation　of　Li2S2.　This　conversion　is　corroborated　by　in　situ　Raman　spectroscopy.　The　FeSe2@C　catalyst　significantly　reduces　the　activation　energy　by　enhancing　charge　transfer　efficiency.　At　a　current　density　of　1C,　the　battery　exhibited　an　initial　capacity　of　581.3　mA　h　g−1,　with　a　remarkable　capacity　retention　of　97.5%　after　600　cycles　and　a　minimal　capacity　decay　rate　of　0.004%　per　cycle,　indicative　of　superior　cyclability.　This　research　propels　the　electrocatalysis　of　Li2S　in　the　charging　phase　of　lithium-sulfur　batteries,　thereby　accelerating　the　kinetics　of　the　SOR　and　contributing　to　the　field＇s　progress.　©　2024　The　Royal　Society　of　Chemistry.