<p>Ti₃C₂T_<i>x</i> MXene anodes for lithium-ion batteries (LIBs) frequently face the significant challenge of low energy storage performance because of their sluggish ion transport kinetics, which is closely related to the surface termination chemistry, particularly for the electrochemical undesired hydroxyl terminations. Herein, we propose a melamine (MA) shielding strategy to the hydroxyl terminations of Ti₃C₂T_<i>x</i> MXene (Ti₃C₂T_<i>x</i>/MA) for optimizing its Li⁺ transport and storage behavior, enabling high-performance energy storage of Ti₃C₂T_<i>x</i>. The density functional theory calculations disclose that the electron-rich nitrogen atoms within the triazine ring of MA notably enhance the Li⁺ adsorption capacity at the interfaces of MA and hydroxyl terminations of Ti₃C₂T_<i>x</i>/MA, and meanwhile also increase the distance between Li⁺ and the hydroxyl terminations. This purposive modification of the electrochemical environment reduces the hindrance posed by the hydroxyl terminations on Li⁺ transport and improves the Li⁺ diffusion kinetics, thereby enhancing the electrochemical performance. As a consequence, the as-designed Ti₃C₂T_<i>x</i>/MA as an anode for LIBs achieves a high-rate capability (3 times higher than that of the pristine Ti₃C₂T_<i>x</i> at 10.0 A g⁻¹), and excellent cycling stability (220.1 mAh g⁻¹ at 2.0 A g⁻¹ over 1000 cycles), as well as a wide temperature operation range (−20 °C to 50 °C). This work offers a novel and straightforward strategy to boost the electrochemical performance of MXenes for practical energy storage applications.</p>