The practical application of lithium-sulfur batteries is significantly impeded by the chaotic migration of lithium polysulfides, sluggish redox-reaction kinetics, and pronounced shuttle effect. Herein, a ternary heterostructure (MoS2-x/MoO2/CoP) is developed with a spontaneous built-in electric field (BIEF) and enriched sulfur vacancies. This heterostructure comprises MoS2-x, which has a high adsorption capability and work function; CoP, noted for its low work function and potent catalytic properties; and MoO2, which features a work function between that of MoS2-x and CoP and serves as a bridge with excellent electronic conductivity. An appropriate combination of the catalyst and adsorbent with sulfur vacancies controls the direction of the BIEF, realizing the “adsorption-directed migration-catalytic” reaction mechanism for sulfur species. Specifically, the synergetic effect of the BIEF and sulfur vacancies enhances electron migration from CoP to MoS2-x, which improves the lithium polysulfide (LiPSs) trapping and accelerates the directional migration of LiPSs to CoP, thereby enabling the efficient catalytic conversion of sulfur species. Consequently, batteries equipped with MoS2-x/MoO2/CoP interlayers that contain sulfur vacancies demonstrate an ultrahigh initial specific capacity of 1356.2 mA h g−1 at 0.2 C, maintaining a capacity of 708.3 mAh g−1 after 1000 cycles at 2 C. Even with sulfur loading increased to 7.13 mg cm−2, these batteries display an initial specific capacity of 7.2 mAh cm−2. This work provides a feasible approach for the rational design of vacancy-containing ternary heterostructure catalysts for commercial lithium-sulfur batteries.