Li-O2 batteries are acknowledged as one of the most promising energy systems due to their high energy density approaching that of gasoline, but the poor battery efficiency and unstable cycling performance still hinder their practical application. In this work, hierarchical NiS2 -MoS2 heterostructured nanorods are designed and successfully synthesized, and it is found that heterostructure interfaces with internal electric fields between NiS2 and MoS2 optimized eg orbital occupancy, effectively adjusting the adsorption of oxygenated intermediates to accelerate reaction kinetics of oxygen evolution reaction and oxygen reduction reaction. Structure characterizations coupled with density functional theory calculations reveal that highly electronegative Mo atoms on NiS2 -MoS2 catalyst can capture more eg electrons from Ni atoms, and induce lower eg occupancy enabling moderate adsorption strength toward oxygenated intermediates. It is evident that hierarchical NiS2 -MoS2 nanostructure with fancy built-in electric fields significantly boosted formation and decomposition of Li2 O2 during cycling, which contributed to large specific capacities of 16528/16471 mAh g-1 with 99.65% coulombic efficiency and excellent cycling stability of 450 cycles at 1000 mA g-1 . This innovative heterostructure construction provides a reliable strategy to rationally design transition metal sulfides by optimizing eg orbital occupancy and modulating adsorption toward oxygenated intermediates for efficient rechargeable Li-O2 batteries.