Moderate eg filling for octahedral metal cations (MOh ) is strongly correlated with the electrocatalytic water oxidation performance in the oxides system. Here, the eg fillings of NiOh and FeOh in NiFe2 O4 -based spinel are controllably regulated by introducing an external radical of catalytically inactive MoSx as an electron acceptor via a novel ultrasonic anchored pyrolysis strategy. The electron occupied in eg orbit of MOh emigrates with the amount of MoS hanging on the apical of octahedral sites, and results in a salutary transition from high to medium eg occupancy state, as confirmed by the X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. In addition, benefiting from the abundant unsaturated S atoms in amorphous MoSx , the MOh at the surface furthest activates and consequently shows a superior water oxidation performance. Density functional theory also reveals that the eg fillings of Ni and Fe decrease to 1.4 and 1.2 after MoSx modification, which can effectively reduce the free energy of the OOH* intermediates in the oxygen evolution reaction process. This work opens an avenue for further releasing the electrocatalytic activity of octahedral sites through bridging external phases with rational electron-capturing/donating capability.