The design of catalyst systems with reasonable configuration to alleviate the shuttle effects and strength conversion kinetics of polysulfide (LiPSs) in lithium-sulfur (Li-S) batteries still remains a challenge. Herein, a novel Cu-CeO_2-x heterointerface is constructed by an ion migrating-capturing process. The Cu²⁺dispersed inner the carbon nanofibers (CNF) is controlled released and transferred outside gradually, and finally is captured by the CeO₂ nanoparticles anchored on the CNF surface and form a Cu-CeO_2-x heterointerface. Synergistically, the CeO₂ capture and disperse Cu clusters as a hosting material, while the Cu decoration prevent further aggregation of CeO₂ at harsh reaction conditions. Thus, the orbital interaction between CeO₂ and Cu induce numerous oxygen vacancy and band gap disappearance at the heterointerface, resulting in a lower energy barrier of electron/hole separation and fast electron transfer in the metallic Cu-CeO_2-x composites. Eventually, the Cu-CeO_2-x can accelerate the catalytic conversion of LiPSs and decomposition of Li₂S, and the Li-S cell deliver an excellent performance of 626 mA h g⁻¹ after 800 cycles at a current density of 2 C, with a decay rate of only 0.046 % per cycle. This work reveals the formation mechanism of oxygen vacancy and disappearance of band gap at heterointerface, opening up a new prospect for rational design of various heterogeneous structures for cathode materials.