Exploring electrolytes of high safety is essential to pave the practical route for sodium-ion batteries (SIBs) toward their important applications in large-scale energy storage and power supplies. In this regard, ionogel electrolytes (IEs) have been highlighted owing to their high ionic conductivity, prominent electrochemical and thermal stability, and, more crucially, high interfacial wettability. However, present studies lack an understanding of the interaction of IEs, which determines the ion desolvation and migration. In this article, IEs comprising an SBA-15 host, an ionic liquid, sodium salt, and poly(vinylidene fluoride)-hexafluoro propylene (PVDF-HFP) have been proposed by mechanical ball milling and roller pressing. The component ratio has been optimized based on the balance between ionic conductivity and self-supporting capability of IEs. The optimal IEs showed sufficiently high ionic conductivity (2.48 × 10-3 S cm-1 at 30 °C), wide electrochemical window (up to 4.8 V vs Na+/Na), and high Na+ transference number (0.37). Due to the presence of SBA-15 and an ionic liquid, the IEs exhibited much improved thermal resistance than that of the conventional organic liquid electrolytes (OLEs). Furthermore, Fourier transform infrared (FT-IR) spectroscopy revealed the hydrogen bonding interaction between silanols and the dissolved salts, not only anchoring anions for immobilization but also promoting the dissociation of sodium salts. After being matched with the Na3V2(PO4)3 (NVP) cathode and metallic Na anode, the SIBs presented a specific discharge capacity of up to 110.7 mA h g-1 initially at room temperature with 92% capacity retention after 300 cycles. The improved safety and electrochemical performance provided insights into rationally regulating IEs and their interactions with the prospect of strengthening their practical applications in SIBs.