AbstractLayer‐stacked anatase titania (a‐TiO2) was synthesized with two‐step oxidation of MXene (Ti3C2Tx, T=O, OH, or F). Compared with direct oxidation of MXene in air, the two‐step oxidation process involving additional hydrothermal pre‐oxidation could alleviate the anomalous grain growth of TiO2, and largely keep the fine structure of MXene. The layered structure derived from MXene enabled the synthesized a‐TiO2 to exhibit superior electrochemical properties. Its discharge capacities reached 241.9 and 131.1 mA h g−1 at the current rates of 0.3 and 12 C, respectively. Even after 10 000 cycles at 6 C, its capacity remained at 107.1 mA h g−1, which is approximately 70 % of the initial capacity. Cyclic voltammetry analysis showed that both diffusive lithium storage in the bulk and interfacial (pseudocapacitive) lithium storage at the surface of layer‐stacked a‐TiO2 contributed to its electrochemical properties.