AbstractMagnesium (Mg) batteries hold promise as a large‐scale energy storage solution, but their progress has been hindered by the lack of high‐performance cathodes. Here, we address this challenge by unlocking the reversible four‐electron Te0/Te4+ conversion in elemental Te, enabling the demonstration of superior Mg//Te dual‐ion batteries. Specifically, the classic magnesium aluminum chloride complex (MACC) electrolyte is tailored by introducing Mg bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), which initiates the Te0/Te4+ conversion with two distinct charge‐storage steps. Te cathode undergoes Te/TeCl4 conversion involving Cl− as charge carriers, during which a tellurium subchloride phase is presented as an intermediate. Significantly, the Te cathode achieves a high specific capacity of 543 mAh gTe−1 and an outstanding energy density of 850 Wh kgTe−1, outperforming most of the previously reported cathodes. Our electrolyte analysis indicates that the addition of Mg(TFSI)2 reduces the overall ion‐molecule interaction and mitigates the strength of ion‐solvent aggregation within the MACC electrolyte, which implies the facilized Cl− dissociation from the electrolyte. Besides, Mg(TFSI)2 is verified as an essential buffer to mitigate the corrosion and passivation of Mg anodes caused by the consumption of the electrolyte MgCl2 in Mg//Te dual‐ion cells. These findings provide crucial insights into the development of advanced Mg‐based dual‐ion batteries.