The sluggish Na+ reaction kinetics with carbon materials limits the fast-charging capability, Coulombic efficiency, and cycle life of sodium-ion batteries, especially at low temperatures. Herein, free-standing carbon nanofiber films, with controllable crystallinity and surface chemistry, are used as a platform to investigate the correlation between Na+ reaction kinetics, storage mechanism, and electrolyte environment. The ion solvation effect and solid-electrolyte interphase (SEI) properties determine the kinetics and storage mechanism. A strong Na+-solvent interaction, such as Na+-diglyme, tends to form a “pseudo-SEI” layer dominated by anion decomposition, enabling fast Na+-solvent co-intercalation kinetics. Tuning the SEI chemistries by pre-cycling in the weakly solvated electrolyte (e.g., ester electrolyte), the intercalation capacity rapidly disappears due to the high energy barrier for Na+ transport. Such mechanistic insights allow us to develop the optimal combination of electrode materials and electrolyte chemistry to achieve high initial Coulombic efficiency, ultra-long cycle life under fast charging, and excellent low-temperature performance.