Lithium–sulfur batteries (LSBs) are promising energy storage systems, but their practical application is hindered by the polysulfide shuttle effect and slow redox kinetics. To address these challenges, we constructed ZIF-67@CoSx/MoO3 with a core–shell structure and CoSx/MoO3 with a hollow structure as separator-modified materials for LSBs by varying the degree of sulfidation of ZIF-67. The high intrinsic conductivity of CoSx facilitated ion transfer between the cathode and separator. Additionally, the introduction of MoO3 formed a heterogeneous structure with CoSx that enhanced the adsorption of LiPSs. Via in situ UV-vis and electrochemical impedance spectroscopy testing, we demonstrated the preferred selective trapping and conversion of LiPSs by CoSx/MoO3. As a result of the synergistic effect of the bimetallic heterogeneous structure, the modified LSB exhibited excellent cycling stability, with a capacity decay rate of only 0.041% after 500 cycles at 1C. Moreover, it achieved a high discharge capacity of 632 mA h g−1 at 2C. This work provides a novel concept for MOF-derived heterogeneous structures to be applied in high-performance LSBs.