<p>Tailoring the catalytic activity of transition-metal oxides (TMOs) through precise electronic structure modulation is a promising strategy to overcome the technical challenges of lithium-sulfur (Li-S) batteries, while it remains a formidable challenge to establish a fundamental structure-property relationship for TMOs. Herein, a strategy of precisely regulating the superexchange interaction in TM–O–TM units of TMOs is proposed to accelerate the redox kinetics of lithium polysulfides (LiPSs) for Li-S batteries. By incorporating Co into NiO lattice (Co-NiO), asymmetric Co–O–Ni units are constructed, which effectively moderate the originally strong superexchange interaction in Ni–O–Ni units. Theoretical and experimental analyses reveal that the weakened Co–O–Ni superexchange interaction enhances the electron delocalization within the coordination units, leading to accelerated interfacial electron transfer kinetics and lowered energy barrier for LiPSs conversion, accompanied by improved structural stability. Accordingly, the Li-S batteries assembled with Co-NiO exhibit a high initial specific capacity of 1229.1 mAh g⁻¹ at 0.2 C and a superior areal capacity of 9.81 mAh cm⁻² with a sulfur loading of 9.44 mg cm⁻². The established correlation between superexchange manipulation and LiPSs redox kinetics provides a promising avenue for developing high-performance Li-S batteries.</p>