Covalent organic frameworks (COFs) have attracted broad interest in a number of fields including gas access, catalysis, and ionic adsorption. However, owing to the low stability in water, the application of COFs in the field of oil/water separation is extensively impeded. In this paper, we synthesized COF-DhaTab/polyacrylonitrile (PAN) nanofibrous composite membranes with a bioinspired spindle-knotted structure via a facile blending electrospinning method. The COF-DhaTab/PAN composite membrane shows prewetting-induced supero-leophobicity under water and super-hydrophobicity under oil. It possesses outstanding rejection ratio (>99.9%), excellent antifouling performance, and ultra- high oil/water mixture flux up to 4229.29 L/m(2) h even though driven only by gravity. Specifically, an extraordinary oil contact angle under water (152.3 degrees) and a satisfied water contact angle under oil (153.7 degrees) were offered by the composite membrane. These are mainly attributed to the spindle-knotted structures induced by COFs. To the best of our knowledge, the application of COF/PAN composite membrane in the field of oil/water separation has never been reported. It is an innovative approach for oily wastewater treatment and oil purification.