Li-ion batteries rely on the use of insertion positive electrodes with performances scaling with the redox potential of the 3D metals accompanying Li-uptake/removal. Although not commonly studied, the Cu2+/Cu3+ redox potential has been predicted from theoretical calculations to possibly offer a high operating voltage redox couple. We herein report the synthesis and crystal structure of a hitherto-unknown oxysulfate phase, Li2Cu2O(SO4)2, which contains infinite edge-sharing CuO4 chains and presents attractive electrochemical redox activity with respect to Li+/Li, namely amphoteric characteristics. Li2Cu2O(SO4)2 shows redox activity at 4.7 V vs Li+/Li0 corresponding to the oxidation of Cu2+ to Cu3+ enlisting ligand holes and associated with the reversible uptake-removal of 0.3 Li. Upon reduction, this compound reversibly uptakes ∼2 Li at an average potential of about 2.5 V vs Li+/Li0, associated with the Cu2+/Cu+ redox couple. The mechanism of the reactivity upon reduction is discussed in detail, with particular attention to the occasional appearance of an oscillation wave in the discharge profile. Our work demonstrates that Cu-based compounds can indeed be fertile scientific ground in the search for new high-energy-density electrodes.