Abstract: | A molecular design strategy is used to construct ordered mesoporous Ti3+‐doped Li4Ti5O12 nanocrystal frameworks (OM‐Ti3+‐Li4Ti5O12) by the stoichiometric cationic coordination assembly process. Ti4+/Li+‐citrate chelate is designed as a new molecular precursor, in which the citrate can not only stoichiometrically coordinate Ti4+ with Li+ homogeneously at the atomic scale, but also interact strongly with the PEO segments in the Pluronic F127. These features make the co‐assembly and crystallization process more controllable, thus benefiting for the formation of the ordered mesostructures. The resultant OM‐Ti3+‐Li4Ti5O12 shows excellent rate (143 mAh g?1 at 30 C) and cycling performances (<0.005 % fading per cycle). This work could open a facile avenue to constructing stoichiometric ordered mesoporous oxides or minerals with highly crystalline frameworks. |