<p>Building anion-derived solid electrolyte interphase (SEI) with enriched LiF is considered the most promising strategy to address inferior safety features and poor cyclability of lithium-metal batteries (LMBs). Herein, we discover that, instead of direct electron transfer from surface polar groups to bis(trifluoromethanesulfonyl)imide (TFSI⁻) for inducing a LiF-rich SEI, the dipole-induced fluorinated-anion decomposition reaction begins with the adsorption of Li ions and is highly dependent on their mobility on the polar surface. To demonstrate this, a single-layer graphdiyne on MXene (sGDY@MXene) heterostructure has been successfully fabricated and integrated into polypropylene separators. It is found that the adsorbed Li ions connect electron-donating sGDY@MXene to TFSI⁻, facilitating interfacial charge transfer for TFSI⁻ decomposition. However, this does not capture the entire picture. The sGDY@MXene also renders the adsorbed Li ions with high mobility, enabling them to reach optimal reaction sites and expedite their coordination processes with O on O=S=O and F on the broken –CF₃⁻, facilitating bond cleavage. In contrast, immobilized Li ions on the more lithiophilic pristine MXene retard these cleavage processes. Consequently, the decomposition reaction is accelerated on sGDY@MXene. This work highlights the dedicate balance between lithiophilicity and Li-ion mobility in effectively promoting a LiF-rich SEI for the long-term stability of LMBs.</p>