Sulfur　cathodes　offer　a　promising　solution　for　high-energy-density,　cost-effective,　and　sustainable　energy　storage.　However,　their　practical　application　is　limited　by　sluggish　and　complex　multistep　sulfur　redox　reactions　(SRRs),　involving　both　electrochemical　and　chemical　processes.　Herein,　it　is　demonstrated　that　accelerating　electrochemical　processes,　particularly　Li2S　nucleation,　over　competing　chemical　pathways　is　fundamental　to　minimizing　sulfur　loss　and　achieving　high-rate　performance.　To　this　end,　a　scalable　and　cost-effective　strategy　is　presented　for　synthesizing　a　series　of　3d　transition　metal-bismuth　(TM-Bi)　atomic　pairs　anchored　on　carbon　nitride　(CN)　and　investigate　their　potential　to　activate　SRRs　in　lithium-sulfur　batteries　(LSBs).　An　initial　screening　identifies　Ni-Bi/CN　and　Co-Bi/CN　as　highly　effective　in　improving　rate　performance.　Detailed　analysis　shows　these　catalysts　promote　direct　electrochemical　transitions　and　rapid　Li2S　nucleation　over　competing　chemical　reactions,　enabling　high　charge-discharge　rates　while　preventing　active　material　loss　and　enhancing　stability.　Electrochemical　analysis,　density　functional　theory,　and　operando　spectroscopy　reveal　that　TM-Bi　pairing　shifts　d-band　states　closer　to　the　Fermi　level　and　modulates　HOMO-LUMO　levels,　promoting　lithium　polysulfide　(LiPS)　interaction　and　facilitating　efficient　charge　transfer.　These　findings　offer　valuable　insights　for　designing　advanced　catalysts　for　LSBs　and　broader　electrocatalytic　applications.