Polyaryletherketones (PAEKs) are a class of ultrahigh performance polymers with outstanding temperature and chemical resistance. Poly(ether ketone ketone) copolymer (Kepstan®) and poly(ether ether ketone) (PEEK) display intrinsic insolubility in nearly all organic solvents. The primary issue for the application of these polymers is their processability which requires a high temperature/pressure-based technique, or the use of harsh and corrosive solvents, like methanesulfonic and sulfuric acid, resulting in sulfonation of the polymer backbone that adversely might affect their chemical stability. In this work, we propose a method to prepare porous Kepstan® and PEEK membranes using N-methyl-2-pyrrolidone (NMP) as solvent at room temperature. It consisted of a modification-regeneration strategy to turn commercial semi-crystalline Kepstan® and PEEK into dithiolane soluble derivatives that allow the fabrication of hollow fiber, flat-sheet, and electrospun nanofibers. The resulting membranes are then regenerated to the solvent-resistant materials. The novel Kepstan® and PEEK hollow fibers exhibited a N,N-dimethylformamide (DMF) permeance of 2.21 and 2.05 L m−2 h−2 bar−1, with more than 90% rejection of Crystal Violet (408 g mol−1) and Methyl Orange (327 g mol−1), respectively.