The practical application of Li–S batteries is severely limited due to low sulfur utilization, sluggish sulfur redox kinetics, intermediate polysulfide dissolution/shuttling, and subsequent anode degradation. A smart cathode with efficient electrocatalyst and a protected anode is necessary. Herein, hollow carbon (HC) spheres are used as a sulfur host to improve the electrical conductivity and buffer the volume expansion of active materials. Considering the weak interaction between carbon and lithium polysulfides (LiPS), tungsten diboride (WB₂) nanoparticles are used as a conductive additive. Both experimental and density functional theory (DFT) comprehensively exhibit that metallic WB₂ nanoparticles can firmly anchor the LiPS through B–S bond formation, accelerate their electrocatalytic conversion, and immobilize them. DFT also reveals that boron interacts with LiPS either through molecular or dissociative adsorption depending on its boron layer arrangement in WB₂. Further, a freestanding lithiated-poly(4-styrene sulfonate) membrane constructed on lithium, offers a homogeneous Li-ion flux, stable interface, and protection from LiPS. Finally, cells with the HC-S+WB₂  cathode and protected anode exhibit improved active material utilization, superior rate performance, and impressive cycling stability, even at high sulfur loading and less quantity of the electrolyte. Further, the pouch cells demonstrate high reversible capacity and an excellent capacity retention.