A detailed investigation on the chemical composition of the cubic form of titanium oxyfluoride-based compound reveals the presence of OH groups substituting the oxide/ fluoride sublattice. The substitution of oxide by hydroxyl groups induces the presence of titanium vacancies () which were characterized by solid-state 1 H and 19 F NMR. 1 H NMR shows that OH groups are present as bridging Ti-OH-Ti or terminal OH groups, i.e. sitting close to a titanium vacancy Ti-OH-. The electrochemical properties vs. Li + /Li indicates that the presence of OH groups prevents the intercalation of lithium in the upper voltage region (1.2-3V vs. Li + /Li). Indeed, a partial dehydroxylation of the framework enables to improve the reversibility of the lithium insertion/de-insertion processes. Since the presence of OH groups in this type of compounds is usual and depends on the synthesis method employed, this work enables to rationalize the different electrochemical behaviours reported in the literature and further highlights the importance of a good knowledge of the chemical composition with regard to the physico-chemical properties.