Despite the potential formation of a strongly stable SEI on the sodium metal surface, even minimal penetration of water molecules into the interfacial region can pose a significant risk of water decomposition on this highly electropositive electrode. Hence, in the absence of free water molecules, we examined the potential presence of water within the interfacial layer as part of ion solvation shells. Our simulations indicate that the solvated ion structures exhibit energetic unfavorability when approaching the sodium surface. This strongly suggests an absence of water in close proximity to the electrode surface, effectively ensuring electrochemical stability. Additionally, our findings indicate a notable charge transfer between the sodium surface and the adsorbed cations and anions, leading to a weakening of the electrostatic attraction between cations and anions in the interfacial region. This could potentially enhance the cation intercalation process, thereby ensuring efficient charge and discharge cycles. Consequently, despite the challenges associated with their highly reactive nature, sodium metal electrodes hold promise for delivering desirable characteristics when coupled with an NaOTF WiS electrolyte.