Searches for new electrode materials for batteries must comply on financial and environmental costs to be useful in practical devices. The sol-gel chemistry has been widely used to design and implemented new concepts for the emergence of advanced materials such as hydride organic-inorganic composites. Here, we show that the simple reaction system including titanium alkoxide and water can be used to stabilize a new class of electrode materials. By investigating the crystallization path of anatase TiO 2 , an X-ray amorphous intermediate phase has been identified whose local structure probed by the pair distribution function, 1 H solid-state NMR and DFT calculations, consists of a layered-type structure as found in the lepidocrocite. This phase presents the following general formula Ti 2-x x O 4-4x (OH) 4x .nH 2 O (x ∼ 0.5) where the substitution of oxide by hydroxide anions leads to the formation of titanium vacancies () and H 2 O molecules are located in interlayers. Solid-state 1 H NMR has enabled to characterize three main hydroxide environments that are Ti-OH, Ti 2 2-OH and Ti 3-OH and layered H 2 O molecules. The electrochemical properties of this phase were further investigated versus lithium and is shown to be very promising with reversible capacities of around 200 mAh.g-1 and an operating voltage of 1.55 V. We further showed that the lithium intercalation proceeds via a solidsolution mechanism. 7 Li solid-state NMR and DFT calculations allowed to identify lithium host sites that are located at the titanium vacancies and interlayer space with lithium being solvated by structural water molecules. The easy fabrication, the absence of lithium and easier recycling and the encouraging properties makes this class of materials very attractive for competitive electrodes for batteries. We thus demonstrate that the revisit of an "old" chemistry with advanced characterization tools allows discovering new materials of technological relevance.