Transition metal oxides (TMOs) are recognized as high-efficiency electrocatalyst systems for restraining the shuttle effect in lithium-sulfur (Li−S) batteries, owing to their robust adsorption capabilities for polysulfides. However, the sluggish catalytic conversion of Li₂S redox and severe passivation effect of TMOs exacerbate polysulfide shuttling and reduce the cyclability of Li−S batteries, which significantly hinders the development of TMOs electrocatalysts. Here, through the anion-cation doping approach, dual incorporation of phosphorus and molybdenum into MnO₂ (P,Mo-MnO₂) was engineered, demonstrating effective mitigation of the passivation effect and allowing for the simultaneous immobilization of polysulfides and rapid redox kinetics of Li₂S. Both experimental and theoretical investigations reveal the pivotal role of dopants in fine-tuning the d-band center and optimizing the electronic structure of MnO₂. Furthermore, this well-designed configuration processes catalytic selectivity. Specifically, P-doping expedites rapid Li₂S nucleation kinetics by minimizing reaction-free energy, while Mo-doping facilitates robust Li₂S dissolution kinetics by mitigating decomposition barriers. This dual-doping approach equips P,Mo-MnO₂ with robust bi-directional catalytic activity, effectively overcoming passivation effect and suppressing the notorious shuttle effect. Consequently, Li−S batteries incorporating P,Mo-MnO₂-based separators demonstrate favorable performance than pristine TMOs. This design offers rational viewpoint for the development of catalytic materials with superior bi-directional sulfur electrocatalytic in Li−S batteries.