Post-polymerization modification (PPM) of polymers is extremely beneficial in terms of designing brand new synthetic pathways toward functional complex polymers. Fortunately, the new developments in the field of organic chemistry along with controlled/living radical polymerization (CLRP) techniques have enabled scientists to readily design and synthesize the functionalized-polymers for wide range of applications via the PPM. In this regard, the reactivity of para-fluorine atom in the fluorinated aromatic structures toward the nucleophilic substitution reactions has made the polymers possessing this group to become a very strong candidate that can undergo efficient PPM. Besides, it has been proven that the thiol-functionalized compounds react with the para-fluorine atom of the pentafluorophenyl group more rapidly and efficiently than the amine- and the hydroxyl-functionalized compounds. Furthermore, the milder experimental conditions to achieve quantitative conversions have led to the reaction between the thiol and the structures possessing pentafluorophenyl groups to be referred to as a click-type reaction. Given this information, this review article aims to present the scientific developments regarding the thiol-para-fluoro click (TPF-click) chemistry, and its impact on PPM to construct novel polymeric structures. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1181-1198