AbstractA solid‐state electrolyte (SSE), which is a solid ionic conductor and electron‐insulating material, is known to play a crucial role in adapting a lithium metal anode to a high‐capacity cathode in a solid‐state battery. Among the various SSEs, the single Li‐ion conductor has advantages in terms of enhancing the ion conductivity, eliminating interfacial side reactions, and broadening the electrochemical window. Covalent organic frameworks (COFs) are optimal platforms for achieving single Li‐ion conduction behavior because of well‐ordered one‐dimensional channels and precise chemical modification features. Herein, we study in depth three types of Li‐carboxylate COFs (denoted LiOOC‐COFn, n = 1, 2, and 3) as single Li‐ion conducting SSEs. Benefiting from well‐ordered directional ion channels, the single Li‐ion conductor LiOOC‐COF3 shows an exceptional ion conductivity of 1.36 × 10−5 S cm−1 at room temperature and a high transference number of 0.91. Moreover, it shows excellent electrochemical performance with long‐term cycling, high‐capacity output, and no dendrites in the quasi‐solid‐state organic battery, with the organic small molecule cyclohexanehexone (C6O6) as the cathode and the Li metal as the anode, and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.