Li-ion batteries are key electric energy storage devices due to high energy density and long cycling lifetime, being widely used in portable electronic devices and large scale systems. In spite of stable cycling performance, the graphite electrode suffers from a low capacity. It is demonstrated in this context that oxygen doping makes MgCl2 electrochemically active. Importantly, the doped structure delivers a high capacity of 941 mAh g−1 for the bulk and 1098 mAh g−1 for the monolayer. The diffusion barrier is calculated to be lower than 0.6 eV. Hexagons and octahedrons composed of Li and Cl atoms are gradually formed with increasing Li coverage, breaking the Mg–Cl bonds. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim