A fluoride-mediated double SNAr polycondensation method was successfully developed to prepare high-molecular weight polymers of intrinsic microporosity (PIMs). The polymerization was conducted between a t-butyldimethylsilyl (TBS)-protected biscatechol monomer (2) and a widely used tetrafluoro monomer (3) in the presence of fluoride ion with excellent to quantitative yields. Three fluoride ion sources (i.e. KF, TBAF and CsF) were investigated, and all of them were effective as catalysts to give high-molecular weight linear products with good film forming property. Therefore, this method warrants its synthetic utility for PIM synthesis. (C) 2015 Elsevier Ltd. All rights reserved.