Despite being a key concept in chemistry, aromaticity and the switching thereof have only seldom been used in charge storage devices. Herein, this work explores how aromaticity switching in a tetraoxa[8]circulene derivative, named N-TOC, can be used in sodium-ion batteries and assesses the switching mechanism through computational approaches. N-TOC delivers exceptional cycling stability at 50 and 100 mA g−1 over 500 cycles with a capacity retention of 91% and 89%. Supported by DFT calculations, this work investigates changes in aromatic motifs within N-TOC through changes in redox states upon charge storage, thus presenting a promising strategy for the design of organic electrodes in Na-ion batteries.