Solid-state electrolyte (SSE) is crucial for a high-performance all-solid-state battery. Here, a new solid sodium electrolyte based on the ionic liquid EIMS-NaTFSI and one metal–organic framework (MOF) UiO-67-MIMS functionalized with zwitterion groups MIMS was obtained (UiO-67 and was assembled with 4,4′-biphenyldicarboxylate linker and cluster Zr₆O₄(OH)₄) (EIMS = 1-(1-ethyl-3-imidazolio)propane-3-sulfonate, NaTFSI = sodium bis(trifluoromethanesulfonyl)imide, MIMS = 1-(1-mthyl-3-imidazolio)propane-3-sulfonate). By contacting and pairing EIMS-NaTFSI (abbreviated as EN-1) to the MIMS group on the framework, EN-1 was directed and arranged along the channels within UiO-67-MIMS, forming a solid composite EN-1@UiO-67-MIMS with Bragg scatter, i.e., a crystalline ionic liquid containing Na⁺ salts (NaTFSI). Such an ionic liquid EN-1@UiO-67-MIMS bearing crystalline MOF matrix showed and preserved fast ion conduction (1.02 × 10⁻² S cm⁻¹) at 150 °C even after 30 days, and exhibited 1–2 orders of magnitude higher conductivities than the bulk ionic liquid EN-1 within a wide temperature range, although the ion content in the latter was higher. The infinite pathway paved by the EN-1 arranged and contacted the MIMS along the channels within MOF well accounts for the fast ion transmission and the stability of the solid-state electrolyte. Such MOF-based crystalline ionic liquid provides a new strategy for developing high-performance solid-state electrolytes for ions.