Reliable operation of Na‐ion batteries requires a mastering of the interfacial processes governing intercalation kinetics. Ion desolvation, amongst others, is a crucial phenomenon as far as power applications are envisioned. Studying the intricacies of interfacial processes faces experimental challenges. Here the complementary use of electrochemical quartz crystal microbalance (EQCM) and operando infrared fiber evanescent wave spectroscopy (IR‐FEWS) combined with molecular dynamics (MD) simulations is reported to investigate the electrode/electrolyte interface of polyanionic Na‐insertion compounds Na 3 V 2 (PO 4 ) 3 (NVP) and Na 3 V 2 (PO 4 ) 2 F 3 (NVPF). Through screening of various electrolytes that differ in their solvation energy and viscosity, the existence of an unusual mass uptake/depletion signal is demonstrated at the NVP interfaces only, indicative of a dissimilarity in migration kinetics of solvent molecules between NVP and NVPF interfaces as supported by IR‐FEWS. This finding is rationalized by positing that sodium depletion is caused by the unusually rapid ion diffusion within NVP mediated by an intermediate metastable phase, which leads to opposite Na + concentration and free solvent molecule gradients at the interface that causes the unusual and anomalous feature observed on EQCM frequency profiles. This feature does not appear with NVPF showing lower ionic diffusion. Altogether, this fundamental study provides valuable fundamental insights into the interface structuring of insertion compounds depending upon their Na + mobility.