The para-fluoro-thiol click reaction (PFTCR) was utilized to prepare linear and hyperbranched fluorinated poly (aryl ether-thioether). For this purpose, 1,2-bis(perfluorophenoxy)ethane was prepared and reacted with 1,6-hexandithiol and trimethylolpropane tris(3-mercaptopropionate), respectively. While hyperbranched polymers were prepared using 0.5 M concentrations of starting materials at room temperature, the linear polymer syntheses were performed at different reaction temperatures and concentrations. The resulting polymers were mainly characterized by NMR measurements and a very distinct fluorine signals regarding meta- and ortho-positions in the F-19 NMR were found for both polymer topologies. In addition to NMR analyses, both linear and hyperbranched polymers were further characterized by using Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). (C) 2018 Wiley Periodicals, Inc.