Since aluminium is one of the most widely available elements in Earth’s crust, developing rechargeable aluminium batteries offers an ideal opportunity to deliver cells with high energy-to-price ratios. Nevertheless, finding appropriate host electrodes for insertion of aluminium (complex) ions remains a fundamental challenge. Here, we demonstrate a strategy for designing active materials for rechargeable aluminium batteries. This strategy entails the use of redox-active triangular phenanthrenequinone-based macrocycles, which form layered superstructures resulting in the reversible insertion and extraction of a cationic aluminium complex. This architecture exhibits an outstanding electrochemical performance with a reversible capacity of 110 mA h g–1 along with a superior cyclability of up to 5,000 cycles. Furthermore, electrodes composed of these macrocycles blended with graphite flakes result in higher specific capacity, electronic conductivity and areal loading. These findings constitute a major advance in the design of rechargeable aluminium batteries and represent a good starting point for addressing affordable large-scale energy storage.