<p>Heteroatom occupancy plays a key role in the precise modulation of specific material regions by introducing foreign elements into the main material matrix, yet it urgently requires further understanding from a spatial perspective. Herein, we propose a “satellite atom-spinel crystal” concept by synthesizing model catalysts with Fe atoms strategically positioned at two different spatial positions of spinel Co₃O₄ (satellite-Fe at Co₃O₄ (Fe_(Sat)-Co₃O₄) and Fe-doped Co₃O₄ (Co₃Fe_(In)O₄)), through which a new catalytic phenomenon is found. Multidimensional <i>in situ</i> spectroscopies revealed that Fe_(Sat)-Co₃O₄ overcomes the crystal field potential energy (Fe_Sat–O &gt; Fe_Sat–O–Co_Oh) and exhibits 1%_{(Fe atom)} lower impedance than that of Co₃Fe_(In)O₄ due to the resistance-free electron delocalization layer formed in Fe_(Sat)-Co₃O₄, which results in tens of times increase of the turnover frequency and mass activity and then a great reduction in the overpotential by 120 mV when used to catalyze the electrochemical oxygen evolution reaction compared to that of Co₃Fe_(In)O₄. Density functional theory calculations further dynamically reveal the mechanisms governing electron itinerancy modulation. This study not only provides valuable insights into the impact of heteroatomic spatial positioning on material properties but also significantly expands our understanding of atomic manipulation.</p>