The commercial viability of emerging lithium−sulfur batteries (LSBs) remains greatly hindered by short lifespans caused by electrically insulating sulfur, lithium polysulfides (Li2Sn; 1 ≤ n ≤ 8) shuttling, and sluggish sulfur reduction reactions(SRRs). This work proposes the utilization of a hybrid composed of sulfiphilic MoS2 and mayenite electride (C12A7:e−) as a cathode host to address these challenges. Specifically, abundant cement-based C12A7:e− is the most stable inorganic electrode, possessing the ultimate electrical conductivity and low work function. Through density functional theory simulations, the key aspects of the MoS2/C12A7:e− hybrid including electronic properties, interfacial binding with Li2Sn, Li+ diffusion, and SRR have been unraveled. Our findings reveal the rational rules for MoS2 as an efficient cathode host by enhancing its mutual electrical conductivity and surface polarity via MoS2/C12A7:e−. The improved electrical conductivity of MoS2 is attributed to the electron donation from C12A7:e− to MoS2, yielding a semiconductor-to-metal transition. The resultant band positions of MoS2/C12A7:e− are well matched with those of conventional current-collecting materials (i.e., Cu and Ni), electrochemically enhancing the electronic transport. Theaccepted charge also intensifies MoS2 surface polarity for attracting polar Li2Sn by forming stronger bonds with Li2Sn via ionic Li−Sbonds than electrolytes with Li2Sn, thereby preventing polysulfide shuttling. Importantly, MoS2/C12A7:e− not only promotes rapid reaction kinetics by reducing ionic diffusion barriers but also lowers the Gibbs free energies of the SRR for effective S8-to-Li2Sconversion. Beyond the reported applications of C12A7:e−, this work highlights its functionality as an electrode material to boost the efficiency of LSBs.