Rapid economic development has led to oil pollution and energy shortage. Membrane separation has attracted much attention due to its simplicity and efficiency in oil-water-separation. The development of membrane materials with enhanced separation properties is essential to improve the separation-efficiency. Proton exchange membrane fuel cells (PEMFCs) are expected to replace conventional engines due to their high-power-conversion rates and other favorable properties. Anhydrous-proton-conductingmaterials are vital components of PEMFCs. However, developing stable proton-conducting materials that exhibit high conductivity at varying temperatures remains challenging. Herein, two covalent organic frameworks (COFs) with long-side-chains are synthesized, and their corresponding COF@SSN membranes. Both membranes can effectively separate oil-water mixtures and water-in-oil emulsions. The TFPT-AF membrane achieves a maximum oil-flux of 6.05×105g h-1 m-2 with an oil-water separation efficiency of above 99%, which is almost unchanged after 20 consecutive uses. COF@H3PO4 doped with different ratios of H3PO4 is prepared, the results show that the perfluorocarbon-chain system has excellent anhydrous proton conductivity, achieving an ultra-high proton-conductivityof 3.98×10-1Scm-1 at 125°C. This study lays the foundation for tailor-made-functionalization of COF through pre-engineering and surface-modification, highlighting the great potential of COFs for oil-water separation and anhydrous-proton-conductivity.