Pervaporation is considered to have great application potential in the field of organic solvent dehydration. However, the development of pervaporation is hampered by the separation performance of current membranes. In this study, covalent organic framework pervaporation membranes were fabricated through contra-diffusion self-assembly strategy for organic solvent dehydration. The polyacrylonitrile (PAN) substrates were pretreated by oxygen plasma to control the diffusion rate and confine the reactive region. Superoxide radicals were generated on the surface of the PAN substrate to assist the growth of TpPa. Therefore, the time of contra-diffusion was shortened to obtain a TpPa membrane, which exhibited a superior separation factor of 1491 and a high permeation flux of 2530 g m-2 h-1 for 90 wt% isopropanol/water mixture. The separation performance of the TpPa membrane could be stable for over 100 h, exhibiting great potential in organic solvent dehydration.