The introduction of materials with dual-functionalities, i.e., the catalytic (adsorption) features to inhibit shuttle effects at the cathode side, and the capability to facilitate homogenous Li-ion fluxes at the anode side, is a promising strategy to realize high performance lithium-sulfur batteries (LSBs). Herein, a facile and rational organic “ligand-induced” (trimesic acid (TMA)) transformation tactic is proposed, which achieves the regulation of electronic performance and d-band center of bimetallic oxides (NiFe₂O₄) to promote bidirectional sulfur conversion kinetics and stabilize the Li plating/striping during the charge/discharge process. The battery assembled with NiFe₂O₄-TMA modified separator exhibits a remarkable initial specific capacity of 1476.6 mAh·g⁻¹ at 0.1 C, outstanding rate properties (661.1 mAh·g⁻¹ at 8.0 C), and excellent cycling ability. The “ligand-induced” transformation tactic proposed in this work will open a whole new possibility for tuning the electronic structure and d-band center to enhance the performance of LSBs