The structure of bulk and nondefective compounds is generally described with crystal models built from well mastered techniques such the analysis of an X-ray diffractogram. The presence of defects, such as cat-ionic vacancies, locally disrupt the long-range order, with the appearance of local structures with order extending only a few nanometers. To probe and describe the electrochemical properties of cation-deficient anatase, we investigated a series of materials having different concentrations of vacancies, i.e., Ti 1−x−y □ x+y O 2−4(x+y) F 4x (OH) 4y , and compared their properties with respect to defect-free stoichiometric anatase TiO 2. At first, we characterized the series of materials Ti 1−x−y □ x+y O 2−4(x+y) F 4x (OH) 4y by means of pair distribution function (PDF), 19 F nuclear magnetic resonance (NMR), Raman and X-ray photoelectron spectroscopies, to probe the compositional and structural features. Second, we characterized the insertion electrochemical properties vs metallic lithium where we emphasized the beneficial role of the vacancies on the cyclability of the electrode under high Crate , with performances scaling with the concentration of vacancies. The improved properties were explained by the change of the lithium insertion mechanism due to the presence of the vacancies, which act as host sites and suppress the phase transition typically observed in pure TiO 2 , and further favor diffusive transport of lithium within the structure. NMR spectroscopy performed on lithiated samples provides evidence for the insertion of lithium in vacancies. By combining electrochemistry and DFT-calculations , we characterized the electrochemical signatures of the lithium insertion in the vacancies. Importantly, we found that the insertion voltage largely depends on the local anionic environment of the vacancy with a fluoride and hydroxide-rich environments , yielding high and low insertion voltages, respectively. This work further supports the beneficial use of defects engineering in electrodes for batteries and provides new fundamental knowledge in the insertion chemistry of cationic vacancies as host sites.