Multivalent batteries show promising prospects for next‐generation sustainable energy storage applications. Herein, we report a polytriphenylamine (PTPAn) composite cathode capable of highly reversible storage of tetrakis(hexafluoroisopropyloxy) borate [B(hfip)₄] anions in both Magnesium (Mg) and calcium (Ca) battery systems. Spectroscopic and computational studies reveal the redox reaction mechanism of the PTPAn cathode material. The Mg and Ca cells exhibit a cell voltage >3 V, a high‐power density of ∼∼3000 W kg⁻¹ and a high‐energy density of ∼∼300 Wh kg⁻¹, respectively. Moreover, the combination of the PTPAn cathode with a calcium‐tin (Ca−Sn) alloy anode could enable a long battery‐life of 3000 cycles with a capacity retention of 60 %. The anion storage chemistry associated with dual‐ion electrochemical concept demonstrates a new feasible pathway towards high‐performance divalent ion batteries.
