Contrary to early motivation, the majority of aluminium ion batteries developed to date do not utilise multivalent ion storage; rather, these batteries rely on monovalent complex ions for their main redox reaction. This limitation is somewhat frustrating because the innate advantages of metallic aluminium such as its low cost and high air stability cannot be fully taken advantage of. Here, we report a tetradiketone macrocycle as an aluminium ion battery cathode material that reversibly reacts with divalent (AlCl2+) ions and consequently achieves a high specific capacity of 350 mAh g−1 along with a lifetime of 8000 cycles. The preferred storage of divalent ions over their competing monovalent counterparts can be explained by the relatively unstable discharge state when using monovalent AlCl2+ ions, which exert a moderate resonance effect to stabilise the structure. This study opens an avenue to realise truly multivalent aluminium ion batteries based on organic active materials, by tuning the relative stability of discharged states with carrier ions of different valence states.