Aluminium batteries constitute a safe and sustainable high‐energy‐density electrochemical energy‐storage solution. Viable Al‐ion batteries require suitable electrode materials that can readily intercalate high‐charge Al3+ ions. Here, we investigate the Al3+ intercalation chemistry of anatase TiO2 and how chemical modifications influence the accommodation of Al3+ ions. We use fluoride‐ and hydroxide‐doping to generate high concentrations of titanium vacancies. The coexistence of these hetero‐anions and titanium vacancies leads to a complex insertion mechanism, attributed to three distinct types of host sites: native interstitial sites, single vacancy sites, and paired vacancy sites. We demonstrate that Al3+ induces a strong local distortion within the modified TiO2 structure, which affects the insertion properties of the neighbouring host sites. Overall, specific structural features induced by the intercalation of highly polarising Al3+ ions should be considered when designing new electrode materials for polyvalent batteries.
