Sodium-ion batteries are promising alternatives for lithium-ion batteries due to their lower cost caused by global sodium availability. However, the low Coulombic efficiency (CE) of the sodium metal plating/stripping process represents a serious issue for the Na anode, which hinders achieving a higher energy density. Herein, we report that the Na+ solvation structure, particularly the type and location of the anions, plays a critical role in determining the Na anode performance. We show that the low CE results from anion-mediated corrosion, which can be tackled readily through tuning the anion interaction at the electrolyte/anode interface. Our strategy thus enables fast-charging Na-ion and Na–S batteries with a remarkable cycle life. The presented insights differ from the prevailing interpretation that the failure mechanism mostly results from sodium dendrite growth and/or solid electrolyte interphase formation. Our anionic model introduces a new guideline for improving the electrolytes for metal-ion batteries with a greater energy density.